U.S. patent number 9,221,944 [Application Number 13/140,595] was granted by the patent office on 2015-12-29 for semiconductor materials prepared from dithienylvinylene copolymers.
This patent grant is currently assigned to BASF SE, Polyera Corporation. The grantee listed for this patent is Florian Doetz, Marcel Kastler, Silke Koehler, Ashok Kumar Mishra, Hiroyoshi Noguchi, Subramanian Vaidyanathan. Invention is credited to Florian Doetz, Marcel Kastler, Silke Koehler, Ashok Kumar Mishra, Hiroyoshi Noguchi, Subramanian Vaidyanathan.
United States Patent |
9,221,944 |
Mishra , et al. |
December 29, 2015 |
Semiconductor materials prepared from dithienylvinylene
copolymers
Abstract
Disclosed are new semiconductor materials prepared from
dithienylvinylene copolymers with aromatic or heteroaromatic
.pi.-conjugated systems. Such copolymers, with little or no
post-deposition heat treatment, can exhibit high charge carrier
mobility and/or good current modulation characteristics. In
addition, the polymers of the present teachings can possess certain
processing advantages such as improved solution-processability and
low annealing temperature.
Inventors: |
Mishra; Ashok Kumar (Singapore,
SG), Vaidyanathan; Subramanian (Singapore,
SG), Noguchi; Hiroyoshi (Singapore, SG),
Doetz; Florian (Singapore, SG), Koehler; Silke
(Mannheim, DE), Kastler; Marcel (Mannheim,
DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Mishra; Ashok Kumar
Vaidyanathan; Subramanian
Noguchi; Hiroyoshi
Doetz; Florian
Koehler; Silke
Kastler; Marcel |
Singapore
Singapore
Singapore
Singapore
Mannheim
Mannheim |
N/A
N/A
N/A
N/A
N/A
N/A |
SG
SG
SG
SG
DE
DE |
|
|
Assignee: |
BASF SE (Ludwigshafen,
DE)
Polyera Corporation (Skokie, IL)
|
Family
ID: |
41820350 |
Appl.
No.: |
13/140,595 |
Filed: |
December 16, 2009 |
PCT
Filed: |
December 16, 2009 |
PCT No.: |
PCT/EP2009/067330 |
371(c)(1),(2),(4) Date: |
June 17, 2011 |
PCT
Pub. No.: |
WO2010/079064 |
PCT
Pub. Date: |
July 15, 2010 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20120217482 A1 |
Aug 30, 2012 |
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Foreign Application Priority Data
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|
|
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Dec 18, 2008 [EP] |
|
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08172061 |
Sep 2, 2009 [EP] |
|
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09169242 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F
228/06 (20130101); H01L 51/0043 (20130101); C08G
61/126 (20130101); H01L 51/0036 (20130101); C08K
3/01 (20180101); C08K 5/0008 (20130101); C09K
11/06 (20130101); H01L 51/42 (20130101); H01L
51/0545 (20130101); Y02P 70/50 (20151101); C09K
2211/1416 (20130101); C08G 2261/344 (20130101); C09K
2211/1425 (20130101); H01L 51/0558 (20130101); C08G
2261/3327 (20130101); C09K 2211/1491 (20130101); C08G
2261/3223 (20130101); C08G 2261/92 (20130101); C08G
2261/124 (20130101); C08G 2261/414 (20130101); C08G
2261/364 (20130101); C08G 2261/18 (20130101); C08G
2261/512 (20130101); C08G 2261/91 (20130101); C09K
2211/1458 (20130101); Y02E 10/549 (20130101); Y02P
70/521 (20151101); C08G 2261/5222 (20130101) |
Current International
Class: |
H01L
51/54 (20060101); C09K 11/06 (20060101); H01L
51/00 (20060101); C08G 61/12 (20060101); C08G
75/06 (20060101); H01L 51/05 (20060101); H01L
51/42 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1989169 |
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Jun 2007 |
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CN |
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2 432 837 |
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Jun 2007 |
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GB |
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WO 9404592 |
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Mar 1994 |
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WO |
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2009 098253 |
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Aug 2009 |
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WO |
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Other References
Dierschke et al. "A hybrid polymer of polyaniline and phthalimide
dyes" Synthetic Metals 2006, 156, 433-443. Year of publication:
2006. cited by examiner .
Witzel et al. "New Poly(arylene ethynylene)s Consisting of
Electron-Deficient Aryleneimide Untis" Macromol. Rapid Commun.
2005, 26, 889-894. Date of online publication: May 27, 2005. cited
by examiner .
U.S. Appl. No. 13/266,935, filed Oct. 28, 2011, Karpov, et al.
cited by applicant .
U.S. Appl. No. 13/376,296, filed Dec. 5, 2012, Mishra, et al. cited
by applicant .
U.S. Appl. No. 13/809,496, filed Jan. 10, 2013, Koehler, et al.
cited by applicant .
He, Y., et al.,
"Poly(thienylene-benzothiadiazole-thienylene-vinylene): A narrow
bandgap polymer with broad absorption from visible to infrared
region," Polymer, vol. 50, pp. 5055-5058, (Sep. 6, 2009) XP
026667703. cited by applicant .
Yang, C.-J., et al., "Electronic engergy transfer in new polymer
nanocomposite assemblies," Supramolecular Science, vol. 1, No. 2,
pp. 91-101, (1994) XP 022720573. cited by applicant .
Goldoni, F., et al., "Synthesis and Characterization of New
Copolymers of Thiophene and Vinylene: Poly(thienylenevinylene)s and
Poly(terthienylenevinylene)s with Thioether Side Chains," Journal
of Polymer Science: Part A: Polymer Chemistry, vol. 37, pp.
4629-4639, (1999) XP 008106987. cited by applicant .
Asawapirom, U., et al., "Dialkylfluorene-Oligothiophene and
Dialkylfluorene-Dithienylvinylene Alternating Copolymers,"
Synthesis, No. 9, pp. 1136-1142, (Jul. 1, 2002) XP 001537816. cited
by applicant .
Bouachrine, M., et al., "Synthese de polymeres conjugues par voie
organometallique," J. Chim. Phys., vol. 95, pp. 1176-1179, (1998)
XP 002574083. cited by applicant .
Lee, J., et al., "Emission color tuning of new fluorene-based
alternating copolymers containing low band gap dyes," Synthetic
Metals, vol. 155, pp. 73-79, (Oct. 13, 2005) XP 025270848. cited by
applicant .
Pina, J., et al., "Spectral and Photophysical Studies of
Poly[2,6-(1,5-dioctylnaphthalene)]thiophenes," J. Phys. Chem. C.
vol. 111, pp. 7185-7191, (Apr. 24, 2007) XP 002527470. cited by
applicant .
Beaupre, S., et al., "Fluorene-Based Copolymers for
Red-Light-Emitting Diodes," Advanced Functional Materials, vol. 12,
No. 3, pp. 192-196, (Mar. 2002) XP 001123889. cited by applicant
.
Chung, D.S., et al., "High Performance Amorphous Polymeric
Thin-Film Transistors Based on
Poly[(1,2-bis-(2'-thienyl)vinyl-5',5''-diyl)-alt-(9,9-dioctylfluorene-2,7-
-diyl] Semiconductors," Chem. Mater., vol. 20, pp. 3450-3456, (Apr.
24, 2008) XP 002590151. cited by applicant .
Ong, B.S., et al., "High-Performance Semiconducting Polythiophenes
for Organic Thin-Film Transistors," J. Am. Chem. Soc., vol. 126,
No. 11, pp. 3378-3379, (Mar. 2, 2004). cited by applicant .
McCulloch, I., et al., "Liquid-crystalline semiconducting polymers
with high charge-carrier mobility," Nature Materials, vol. 5, pp.
328-333, (Mar. 19, 2006). cited by applicant .
Pan, H., et al., "Benzodithiophene Copolymer--A Low-Temperature,
Solution-Processed High-Performance Semiconductor for Thin-Film
Transistors," Advanced Functional Materials, vol. 17, pp.
3574-3579, (2007). cited by applicant .
International Search Report issued Jul. 28, 2010 in PCT/EP09/067330
filed Dec. 16, 2009. cited by applicant .
J. H. Burroughes, et al., "Light--Emitting Diodes Based on
Conjugated Polymers", Nature, vol. 347, Oct. 11, 1990, pp. 539-541
(with cover page). cited by applicant .
Arno Kraft, et al., "Electroluminescent Conjugated Polymers-Seeing
Polymers in a New Light", Angew. Chem. Int. Ed., 1998, 37, pp.
402-428. cited by applicant .
H. Fuchigami, et al., "Polythienylenevinylene Thin-Film Transistor
with High Carrier Mobility", Appl. Phys. Lett., 63,(10), Sep. 6,
1993, p. 1372-1374 (with cover page). cited by applicant .
Paulette Prins, et al., "Electron and Hole Dynamics on Isolated
Chains of a Solution-Processable Poly (thienylenevinylene)
Derivative in Dilute Solution", Adv. Mater., 2005, 17, No. 6, pp.
718-723. cited by applicant .
S. Gillissen, et al., "Synthesis of a Processible High Molecular
Weight Poly (Thienylene Vinylene), Polymerisation and Thin-Film
Transistor Properties", Synthetic Metals, 135-136, 2003, pp.
255-256. cited by applicant .
Shingetsu Yamada, et al., "New Conducting Polymer Film:
Poly(2,5-Thienylenevinylene) Prepared Via a Soluble Precursor
Polymer", J. Chem. Soc. Commun., 1987, pp. 1448-1449 (with cover
page). cited by applicant .
Extended Search Report issued Jul. 15, 2013 in European Application
No. 13164964.2. cited by applicant.
|
Primary Examiner: Bohaty; Andrew K
Attorney, Agent or Firm: Oblon, McClelland, Maier &
Neustadt, L.L.P.
Claims
The invention claimed is:
1. A polymer of the formula I: ##STR00113## or of the formula I':
##STR00114## wherein: pi-2 is selected from the group consisting of
repeating units of the formula ##STR00115## R.sup.1, R.sup.2,
R.sup.3, R.sup.4 are selected from the group consisting of H,
halogen, CN, a C.sub.1- 30 alkyl group, a C.sub.2-30 alkenyl group,
a C.sub.1-20 alkoxy group and a C.sub.1-20 alkylthio group;
R.sup.15 and R.sup.16 are selected from the group consisting of H,
halogen, CN, a C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group,
a C.sub.1-20 alkoxy group and a C.sub.1-20 alkylthio group; y'
represents 1; and n represents an integer greater than 1.
2. The polymer according to claim 1, wherein pi-2 is
##STR00116##
3. The polymer according to claim 1, wherein n is an integer
between 2 and 5000.
4. A composition, comprising one or more polymers of claim 1,
dissolved or dispersed in a liquid medium.
5. The composition of claim 4, wherein the liquid medium comprises
water or an organic solvent.
6. The composition of claim 4, the composition further comprising
one or more additives.
7. The composition of claim 6, wherein the one or more additives
are independently selected from the group consisting of a viscosity
modulator, a detergent, a dispersant, a binding agent, a
compatibilizing agent, a curing agent, an initiator, a humectant,
an antifoaming agent, a wetting agent, a pH modifier, a biocide and
a bactereriostat.
8. A thin film semiconductor, comprising one or more polymers of
claim 1.
9. A composite, comprising a substrate and the thin film
semiconductor of claim 8.
10. A field effect transistor device, comprising the thin film
semiconductor of claim 8.
11. A photovoltaic device, comprising the thin film semiconductor
of claim 8.
12. An organic light emitting device, comprising the thin film
semiconductor of claim 8.
13. A field effect transistor device, comprising the composite of
claim 9.
14. A photovoltaic device, comprising the composite of claim 9.
15. An organic light emitting device, comprising the composite of
claim 9.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of PCT/EP2009/067330 filed on
Dec. 16, 2009. This application is based upon and claims the
benefit of priority to European Application No. 08172061.7 filed on
Dec. 18, 2008, and to European Application No. 09169242.6 filed on
Sep. 2, 2009.
BACKGROUND
Since the beginning of the electronic era, the primary building
blocks in electronics and microelectronics have been field-effect
transistors (FETs) based on inorganic electrodes, insulators, and
semiconductors. These materials have proven to be reliable and
highly efficient, providing performance that improves continually
according to Moore's law. More recently, organic materials have
been developed as both active and passive materials in electronic
circuitry. Instead of competing with conventional silicon
technologies, organic FETs (OFETs) based on molecular and polymeric
materials are desired in niche applications, for example, in
low-end radio-frequency technologies, sensors, and light emission,
as well as in integrated optoelectronic devices such as pixel
drives and switching elements in displays. These systems have been
widely pursued for the advantages they offer, which include
processability via vapor/solution-phase fabrication, good
compatibility with different substrates (e.g., flexible plastics),
and opportunities for structural tailoring. This trend is further
driven by the continued demand for low-cost, large-area, flexible
and lightweight devices, and the possibility to process these
materials at much lower substrate temperatures compared to
inorganic semiconductors.
The simplest and most common OFET device configuration is that of a
thin-film transistor (TFT), in which a thin film of the organic
semiconductor is deposited on top of a dielectric with an
underlying gate (G) electrode. Charge-injecting drain-source (D-S)
electrodes providing the contacts are defined either on top of the
organic film (top-configuration) or on the surface of the FET
dielectric prior to the deposition of the semi-conductor
(bottom-configuration). The current between the S and D electrodes
is low when no voltage (V.sub.g) is applied between the G and D
electrodes, and the device is in the so called "off" state. When
V.sub.g is applied, charges can be induced in the semi-conductor at
the interface with the dielectric layer. As a result, current
(I.sub.d) flows in the channel between the S and D electrodes when
a source-drain bias (V.sub.d) is applied, thus providing the "on"
state of a transistor. Key parameters in characterizing FET
performance are the field-effect mobility (.mu.), which quantifies
the average charge carrier drift velocity per unit electric field,
and the current on/off ratio (I.sub.on:I.sub.off), which is the D-S
current ratio between the "on" and "off" states. For a
high-performance OFET, the field-effect mobility and on/off ratio
should both be as high as possible, for example, having at least
.mu..about.0.1-1 cm.sup.2V.sup.-1s.sup.-1 and
I.sub.on/I.sub.off.about.10.sup.6.
Most OFETs operate in p-type accumulation mode, meaning that the
semi-conductor acts as a hole-transporting material. For most
practical applications, the mobility of the field-induced charges
should be greater than about 0.01 cm.sup.2/Vs. To achieve high
performance, the organic semiconductors should satisfy stringent
criteria relating to both the injection and current-carrying
capacity; in particular: (i) the HOMO/LUMO energies of the material
should be appropriate for hole/electron injection at practical
voltages; (ii) the crystal structure of the material should provide
sufficient overlap of the frontier orbitals (e.g., .pi.-stacking
and edge-to-face contacts) to allow charges to migrate among
neighboring molecules; (iii) the compound should be very pure as
impurities can hinder the mobility of charge carriers; (iv) the
conjugated core of the material should be preferentially oriented
to allow charge transport in the plane of the TFT substrate (the
most efficient charge transport occurs along the direction of
intermolecular .pi.-.pi. stacking); and (v) the domains of the
crystalline semiconductor should uniformly cover the area between
the source and drain contacts, hence the film should have a single
crystal-like morphology.
Among the organic p-type semiconductors used in OFETs, the classes
of (oligo, poly)thiophenes and acenes are the most investigated.
For instance, the first report on a polyheterocycle-based FET was
on polythiophene, and poly(3-hexyl)thiophene and
.alpha.,.omega.-alkyloligothiophenes were the first high-mobility
polymer and small molecules, respectively. Over the years, chemical
modifications of the .pi.-conjugated core, variations in
ring-to-ring connectivity and substitution pattern have resulted in
the synthesis and testing of a considerable number of semiconductor
materials with improved mobilities.
In order to take full advantage of the cost effciencies of solution
processing methods such as spin coating, stamping, ink-jet printing
or mass printing such as gravure and offset printing, polymeric
organic semiconductors would seem to be the material of choice.
Among polythiophenes, soluble regioregular polythiophenes such as
poly(3-hexylthiophenes) (P3HT), or
poly(3,3'''-didodecylquaterthiophene),
poly(2,5-bis-(3-dodecylthiophen-2-yl)-thieno-(3,2-b)thiophene,
poly(4,8-didodecyl-2,6-bis-(3-methyl-thiophen-2-yl)-benzo[1,2-b:4,5-b']di-
thiophene) and their variants are most promising for OTFT
applications due to their high charge carrier mobilities. See for
eg. Ong, B. S. et al. J. Am. Chem. Soc. 2004, 126, 3378-3379;
McCulloch, I. et. al. Nat. Mater. 2006, 5, 328-333 and Pan, H. et.
al. Adv. Fund. Mater. 2007, 17, 3574-3579.
Despite recent advances one of the major drawbacks of these
polymers is the need for post deposition annealing to achieve their
high mobilities. The annealing temperature can range from
120.degree. C. to 200.degree. C. for between 15 minutes to a few
hours. For flexible electronics, if the annealing temperature of
organic semiconductor is higher than the glass transition
temperature or melting point of the plastic substrate, then the
substrate softens before the semiconductor mobility is optimized.
Further, adapting even relatively low annealing temperatures for a
prolonged period of time in a reel to reel process involves
significant costs and lower throughput.
Another drawback with the state-of-the-art high performing
semiconductors is the poor solubility in common organic solvents at
room temperature. These polymers are sufficiently soluble only in
high boiling point chlorinated solvents such as dichlorobenzene and
sometimes only at elevated temperature.
Hence, for reel to reel, low cost production of organic
electronics, polymeric semiconductors that can be formulated in
reasonably high concentrations in common organic solvents and that
do not require high and extensive annealing are necessary.
Vinylene moieties in polymers are advantageous as they reduce the
aromaticity of the backbone and hence improve charge
delocalization, leading to lower band gaps, better conjugation and
improved charge transport. Also, the incorporation of vinyl moiety
in the semiconductor backbone is expected to afford a certain
degree of rotational freedom between its neighbouring aromatic
units, which should a priori help to improve the solubility and
hence processability of the polymer and, further, to reduce the
energy requirement for molecular packing in the solid state
(annealing temperature/time). This, in turn offers advantages in
fabricating solution processed electronic components such as OTFTs,
OLEDs and OPVs.
However, the use of vinyl moieties in polymers has been limited to
poly(phenylene vinylenes) and poly(thiophene vinylenes) (PTVs) and
variants which have been synthesized and developed. Among the
earliest reports of semiconducting polymers are
poly(para-phenylenevinylene)s (PPVs) and their derivatives used as
active materials in organic light emitting diodes (OLEDs). See eg.
Burroughes, J. H. et al. Nature 1990, 347, 539-541 and Kraft, A. et
al. Angew. Chem. Int. Ed. 1998, 37, 402-428. PPVs have a relatively
large band gap, and poor hole mobilities. For this reason, PTVs and
its derivatives were adopted for use in OTFTs. See eg. Fuchigami,
H. T. et al. Appl. Phys. Lett. 1993, 63, 1372; Prins, P. et. al
Adv. Mater. 2005, 17, 718; Gillissen, S. et al. Synth. Met. 2003,
135-136, 255 and Yamada, S. J. Chem. Soc., Chem. Commun. 1987,
1448. It is expected that the high proportion of the vinyl bonds
along the polymer backbone makes these polymers disordered in the
solid state and this results in the observed hole mobilities of
only 10.sup.-4-10.sup.-2 cm.sub.2/Ns.
SUMMARY
In light of the foregoing, the present teachings provide organic
semiconductor materials and associated compositions, composites,
and/or devices that can address various deficiencies and
shortcomings of the state-of-the-art, including those outlined
above.
More specifically, the present teachings provide polymers having
semiconducting activity and semiconductor materials prepared from
these polymers, wherein the polymers can be A-B copolymers of
optionally substituted dithienylvinylenes (monomer A) in
conjugation with aromatic or heteroaromatic cyclic moieties
(monomer B). It should be understood that the polymers of the
present teachings can be referred to herein as either polymers or
copolymers. Further, the polymers can be embedded with other
components for utilization in other semiconductor-based devices.
The polymers of the present teachings can be used to prepare either
p-type or n-type semiconductor materials, which in turn can be used
to fabricate various organic electronic articles, structures and
devices, including field-effect transistors, unipolar circuitries,
complementary circuitries, photovoltaic devices, and light emitting
devices.
The polymers of the present teachings can exhibit semiconductor
behavior such as high carrier mobility and/or good current
modulation characteristics in a field-effect device, and light
absorption/charge separation in a photovoltaic device. Similarly,
other organic semiconductor based devices such as OPVs, OLETs, and
OLEDs can be fabricated efficiently using the polymeric materials
described herein. In addition, the present polymers can possess
certain processing advantages such as solution-processability
and/or reduced annealing temperatures/time.
The polymers of the present teachings have the formula I:
##STR00001## or the formula I':
##STR00002## wherein pi-1, pi-2, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, y, y' and n are as defined herein below.
The present teachings also provide methods of preparing such
polymers and semi-conductor materials, as well as various
compositions, composites, and devices that incorporate the polymers
and semiconductor materials disclosed herein.
The foregoing as well as other features and advantages of the
present teachings, will be more fully understood from the following
figures, description, and claims.
BRIEF DESCRIPTION OF DRAWINGS
It should be understood that the drawings described below are for
illustration purpose only. The drawings are not necessarily to
scale and are not intended to limit the scope of the present
teachings in any way.
FIG. 1 shows the .sup.1H NMR spectra of a polymer of the present
teachings (P(T2-12-TVT)), in CD.sub.2Cl.sub.2.
FIG. 2 shows a representative differential scanning calorimetry
thermogram of a polymer of the present teachings (P(T2-12-TVT)),
obtained under nitrogen with a scanning rate of 10.degree.
C./minute.
FIG. 3 illustrates four different configurations of thin film
transistors: a) bottom-gate top contact, b) bottom-gate
bottom-contact, c) top-gate bottom-contact, and d) top-gate top
contact; each of which can be used to incorporate polymers of the
present teachings.
FIG. 4 shows the transistor structure used in Example 3A. Reference
numeral 1 denotes the substrate, reference numeral 2 the dielectric
layer.
FIG. 5 shows an exemplary transfer plot for P(TS8TVT) based
transistors, where the active layer was annealed at 150.degree.
C.
FIG. 6 shows the transistor structure used in Examples 3C-3E.
Reference numeral 1 denotes the substrate, reference numeral 2 the
dielectric layer.
FIG. 7 shows an exemplary transfer plot and the extracted
mobilities for the as-dried P(T2-12-TVT) based transistors (without
any annealing).
FIG. 8a illustrates a representative structure of a
bulk-heterojunction organic photovoltaic device (also known as
solar cell) which can incorporate one or more polymers of the
present teachings as the donor and/or acceptor materials. Reference
numeral 1 denotes the ITO anode, reference numeral 2 the polymer
blend layer and reference numeral 3 the metal cathode.
FIG. 8b illustrates a representative structure of an organic
light-emitting device which can incorporate one or more polymers of
the present teachings as electron-transporting and/or emissive
and/or hole-transporting materials. Reference numeral 1 denotes the
ITO anode, reference numeral 2 the polymer layer and reference
numeral 3 the metal cathode.
Table 1 summarizes the structure, the material for the different
components, and the method of fabrication of various exemplary TFTs
incorporating representative polymers of the present teachings.
Table 2 summarizes the hole mobilities of an exemplary polymer of
the current teachings (P(TS8TVT)) measured for different annealing
temperatures for the semi-conductor under ambient conditions and
compares this with a state-of-the art polymer structure
(P(TS8T2))
DETAILED DESCRIPTION
The present teachings relate to semiconductor materials prepared
from dithienylvinylene based copolymers. The present teachings
further relate to methods for preparing these copolymers and
semiconductor materials, as well as to compositions, composites,
materials, articles, structures, and devices that incorporate such
copolymers and semiconductor materials.
Accordingly, one aspect of the present teachings provides polymers
having semiconducting activity and semiconductor materials prepared
from these polymers. More specifically, the polymers can be A-B
copolymers comprising a first repeating unit (moiety A) that
comprises a dithienylvinylene derivative, and a second repeating
unit (moiety B) that includes one or more electron-accepting or
electron-donating cyclic moieties. Both moiety A and moiety B
typically include an aromatic or otherwise highly conjugated cyclic
(carbocyclic or heterocyclic) core, where such cyclic core can be
optionally substituted or functionalized with one or more
electron-withdrawing, electron-donating and/or solubilizing groups.
The pairing of moieties A and B, and any functionalization on
either moiety can be affected by one or more of the following
considerations: 1) modulation of the majority carrier type
depending on the electronic structure of monomers A and B; 2)
regiochemistry of the polymerization possibly affording
regioregular polymers; 3) the core planarity and linearity of the
polymer chain; 4) the capability of additional functionalization of
the .pi.-conjugated core; 5) the potential for increased solubility
of the polymer for solution processing; 6) achieving strong
.pi.-.pi. interactions/intermolecular electronic coupling; and 7)
capability of the resulting polymer to crystallize at least
partially when processed from solution. The resulting polymers and
related methods can be employed to enhance the performance of an
associated device (e.g., an organic field effect transistor, a
light-emitting transistor, a solar cell, or the like).
Throughout the description, where compositions are described as
having, including, or comprising specific components, or where
processes are described as having, including, or comprising
specific process steps, it is contemplated that compositions of the
present teachings also consist essentially of, or consist of, the
recited components, and that the processes of the present teachings
also consist essentially of, or consist of, the recited processing
steps.
In the application, where an element or component is said to be
included in and/or selected from a list of recited elements or
components, it should be understood that the element or component
can be any one of the recited elements or components and can be
selected from a group consisting of two or more of the recited
elements or components. Further, it should be understood that
elements and/or features of a composition, an apparatus, or a
method described herein can be combined in a variety of ways
without departing from the spirit and scope of the present
teachings, whether explicit or implicit herein.
The use of the terms "include," "includes", "including," "have,"
"has," or "having" should be generally understood as open-ended and
non-limiting unless specifically stated otherwise.
The use of the singular herein includes the plural (and vice versa)
unless specifically stated otherwise. In addition, where the use of
the term "about" is before a quantitative value, the present
teachings also include the specific quantitative value itself,
unless specifically stated otherwise.
It should be understood that the order of steps or order for
performing certain actions is immaterial so long as the present
teachings remain operable. Moreover, two or more steps or actions
may be conducted simultaneously.
As used herein, a "p-type semiconductor material" or "p-type
semiconductor" refers to a semiconducting material, for example, an
organic semiconducting material, having holes as the majority
current carriers. In some embodiments, when deposited on a
substrate, a p-type semiconductor can provide a hole mobility in
excess of about 10.sup.-5 cm.sup.2/Vs. In the case of field-effect
devices, a p-type semiconductor material also should exhibit a
current on/off ratio of greater than about 1000.
As used herein, a "n-type semiconductor material" or "n-type
semiconductor" refers to a semiconducting material, for example, an
organic semiconducting material, having electrons as the majority
current carriers. In some embodiments, when deposited on a
substrate, an n-type semiconductor can provide an electron mobility
in excess of about 10.sup.-5 cm.sup.2/Vs. In the case of
field-effect devices, a n-type semiconductor material also should
exhibit a current on/off ratio of greater than about 1000.
As used herein, "solution-processable" refers to compounds,
materials, or compositions that can be used in various
solution-phase processes including spin-coating, printing (e.g.,
inkjet printing, gravure printing, offset printing), spray coating,
electrospray coating, drop casting, dip coating, and blade
coating.
As used herein, "polymer" or "polymeric compound" refers to a
molecule including at least two or more repeating units connected
by covalent chemical bonds. The polymer or polymeric compound can
have only one type of repeating unit as well as two or more types
of different repeating units. In the former case, the polymer can
be referred to as a homopolymer. In the latter case, the term
"copolymer" or "copolymeric compound" can be used herein instead,
especially when the polymer includes chemically significantly
different repeating units. Unless specified otherwise, the assembly
of the repeating units in the copolymer can be head-to-tail,
head-to-head, or tail-to-tail. In addition, unless specified
otherwise, the copolymer can be a random copolymer, an alternating
copolymer, or a block copolymer.
As used herein, a "fused ring" or a "fused ring moiety" refers to a
polycyclic ring system having at least two rings wherein at least
one of the rings is aromatic and such aromatic ring (carbocyclic or
heterocyclic) has a bond in common with at least one other ring
that can be aromatic or non-aromatic, and carbocyclic or
heterocyclic. These polycyclic ring systems can be highly
.pi.-conjugated and can include polycyclic aromatic hydrocarbons
such as rylenes having the formula:
##STR00003## where a.degree. can be an integer in the range of 0-3;
coronenes having the formula:
##STR00004## where b.degree. can be an integer in the range of 0-3;
and linear acenes having the formula:
##STR00005## where x can be an integer in the range of 0-4. The
fused ring moiety can be optionally substituted as described
herein.
As used herein, a "cyclic moiety" can include one or more (e.g.,
1-6) carbocyclic or heterocyclic rings. In embodiments where the
cyclic moiety is a polycyclic moiety, the polycyclic system can
include one or more rings fused to each other (i.e., sharing a
common bond) and/or connected to each other via a spiro atom. The
cyclic moiety can be a cycloalkyl group, a heterocycloalkyl group,
an aryl group, or a heteroaryl group, and can be optionally
substituted as described herein.
As used herein, "halo" or "halogen" refers to fluoro, chloro,
bromo, and iodo.
As used herein, "alkyl" refers to a straight-chain or branched
saturated hydrocarbon group. Examples of alkyl groups include
methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl),
butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl
groups (e.g., n-pentyl, isopentyl, neopentyl), and the like. In
various embodiments, an alkyl group can have 1 to 20 carbon atoms,
i.e., a C.sub.1-20 alkyl group. In some embodiments, an alkyl group
can have 1 to 6 carbon atoms, and can be referred to as a "lower
alkyl group." Examples of lower alkyl groups include methyl, ethyl,
propyl (e.g., n-propyl and isopropyl), and butyl groups (e.g.,
n-butyl, isobutyl, sec-butyl, tert-butyl). In some embodiments,
alkyl groups can be substituted as disclosed herein. An alkyl group
is generally not substituted with another alkyl group or an alkenyl
or alkynyl group.
As used herein, "haloalkyl" refers to an alkyl group having one or
more halogen substituents. Examples of haloalkyl groups include
CF.sub.3, C.sub.2F.sub.5, CHF.sub.2, CH.sub.2F, CCl.sub.3,
CHCl.sub.2, CH.sub.2Cl, C.sub.2Cl.sub.5, and the like. Perhaloalkyl
groups, i.e., alkyl groups wherein all of the hydrogen atoms are
replaced with halogen atoms (e.g., CF.sub.3 and C.sub.2F.sub.5),
are included within the definition of "haloalkyl." For example, a
C.sub.1-20 haloalkyl group can have the formula --C.sub.mX.sub.2t--
or --C.sub.mH.sub.2m-tX.sub.t--, wherein X is F, Cl, Br, or I, m is
an integer in the range of 1 to 20, and t is an integer in the
range of 0 to 40, provided that m is less than or equal to 2t.
Haloalkyl groups that are not perhaloalkyl groups can be optionally
substituted as disclosed herein.
As used herein, "arylalkyl" refers to an -alkyl-aryl group, wherein
the arylalkyl group is covalently linked to the defined chemical
structure via the alkyl group. An arylalkyl group is within the
definition of an --Y--C.sub.6-14 aryl group, where Y is as defined
herein. An example of an arylalkyl group is a benzyl group
(--CH.sub.2C.sub.6H.sub.5). An arylalkyl group can be optionally
substituted, i.e., the aryl group and/or the alkyl group can be
substituted as disclosed herein.
As used herein, "alkenyl" refers to a straight-chain or branched
alkyl group having one or more carbon-carbon double bonds. Examples
of alkenyl groups include ethenyl, propenyl, butenyl, pentenyl,
hexenyl, butadienyl, pentadienyl, hexadienyl groups, and the like.
The one or more carbon-carbon double bonds can be internal (such as
in 2-butene) or terminal (such as in 1-butene). In various
embodiments, an alkenyl group can have 2 to 20 carbon atoms, i.e.,
a C.sub.2-20 alkenyl group. In some embodiments, alkenyl groups can
be substituted as disclosed herein. An alkenyl group is generally
not substituted with another alkenyl group or an alkyl or alkynyl
group.
As used herein, "alkynyl" refers to a straight-chain or branched
alkyl group having one or more triple carbon-carbon bonds. Examples
of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, and
the like. The one or more triple carbon-carbon bonds can be
internal (such as in 2-butyne) or terminal (such as in 1-butyne).
In various embodiments, an alkynyl group can have 2 to 20 carbon
atoms, i.e., a C.sub.2-20 alkynyl group. In some embodiments,
alkynyl groups can be substituted as disclosed herein. An alkynyl
group is generally not substituted with another alkynyl group or an
alkyl or alkenyl group.
As used herein, "cycloalkyl" refers to a non-aromatic carbocyclic
group including cyclized alkyl, alkenyl, and alkynyl groups. A
cycloalkyl group can be monocyclic (e.g., cyclohexyl) or polycyclic
(e.g., containing fused, bridged, and/or spiro ring systems),
wherein the carbon atoms are located inside or outside of the ring
system. Any suitable ring position of the cycloalkyl group can be
covalently linked to the defined chemical structure. Examples of
cycloalkyl groups include cyclopropyl, cyclopropylmethyl,
cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl,
cyclohexylethyl, cycloheptyl, cyclopentenyl, cyclohexenyl,
cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcaryl,
adamantyl, and spiro[4.5]decanyl groups, as well as their homologs,
isomers, and the like. In some embodiments, cycloalkyl groups can
be substituted as disclosed herein.
As used herein, "heteroatom" refers to an atom of any element other
than carbon or hydrogen and includes, for example, nitrogen,
oxygen, silicon, sulfur, phosphorus, and selenium.
As used herein, "cycloheteroalkyl" refers to a non-aromatic
cycloalkyl group that contains at least one ring heteroatom
selected from O, N and S, and optionally contains one or more
double or triple bonds. One or more N or S atoms in a
cycloheteroalkyl ring can be oxidized (e.g., morpholine N-oxide,
thiomorpholine S-oxide, thiomorpholine S,S-dioxide). In some
embodiments, nitrogen atoms of cycloheteroalkyl groups can bear a
substituent, for example, a hydrogen atom, an alkyl group, or other
substituents as described herein. Cycloheteroalkyl groups can also
contain one or more oxo groups, such as piperidone, oxazolidinone,
pyrimidine-2,4(1H,3H)-dione, pyridin-2(1H)-one, and the like.
Examples of cycloheteroalkyl groups include, among others,
morpholine, thiomorpholine, pyran, imidazolidine, imidazoline,
oxazolidine, pyrazolidine, pyrazoline, pyrrolidine, pyrroline,
tetrahydrofuran, tetrahydrothiophene, piperidine, piperazine, and
the like. In some embodiments, cycloheteroalkyl groups can be
substituted as disclosed herein.
As used herein, "aryl" refers to an aromatic monocyclic hydrocarbon
ring system or a polycyclic ring system in which two or more
aromatic hydrocarbon rings are fused (i.e., having a bond in common
with) together or at least one aromatic monocyclic hydrocarbon ring
is fused to one or more cycloalkyl and/or cycloheteroalkyl rings.
An aryl group can have from 6 to 30 carbon atoms in its ring
system, which can include multiple fused rings. In some
embodiments, a polycyclic aryl group can have from 8 to 14 carbon
atoms. Any suitable ring position of the aryl group can be
covalently linked to the defined chemical structure. Examples of
aryl groups having only aromatic carbocyclic ring(s) include
phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl
(tricyclic), phenanthrenyl (tricyclic), and like groups. Examples
of polycyclic ring systems in which at least one aromatic
carbocyclic ring is fused to one or more cycloalkyl and/or
cycloheteroalkyl rings include, among others, benzo derivatives of
cyclopentane (i.e., an indanyl group, which is a 5,6-bicyclic
cycloalkyl/aromatic ring system), cyclohexane (i.e., a
tetrahydronaphthyl group, which is a 6,6-bicyclic
cycloalkyl/aromatic ring system), imidazoline (i.e., a
benzimidazolinyl group, which is a 5,6-bicyclic
cycloheteroalkyl/aromatic ring system), and pyran (i.e., a
chromenyl group, which is a 6,6-bicyclic cycloheteroalkyl/aromatic
ring system). Other examples of aryl groups include benzodioxanyl,
benzodioxolyl, chromanyl, indolinyl groups, and the like. In some
embodiments, aryl groups can be substituted as disclosed herein. In
some embodiments, an aryl group can have one or more halogen
substituents, and can be referred to as a "haloaryl" group.
Perhaloaryl groups, i.e., aryl groups wherein all of the hydrogen
atoms are replaced with halogen atoms (e.g., --C.sub.6F.sub.5), are
included within the definition of "haloaryl." In certain
embodiments, an aryl group is substituted with another aryl group
and can be referred to as a biaryl group. Each of the aryl groups
in the biaryl group can be substituted as disclosed herein.
As used herein, "heteroaryl" refers to an aromatic monocyclic ring
system containing at least 1 ring heteroatom selected from oxygen
(O), nitrogen (N), sulfur (S), selenium (Se) and arsenic (As) or a
polycyclic ring system where at least one of the rings present in
the ring system is aromatic and contains at least 1 ring
heteroatom. Polycyclic heteroaryl groups include two or more
heteroaryl rings fused together and monocyclic heteroaryl rings
fused to one or more aromatic carbocyclic rings, non-aromatic
carbocyclic rings, and/or non-aromatic cycloheteroalkyl rings. A
heteroaryl group, as a whole, can have, for example, from 5 to 14
ring atoms and contain 1-5 ring heteroatoms. The heteroaryl group
can be attached to the defined chemical structure at any heteroatom
or carbon atom that results in a stable structure. Generally,
heteroaryl rings do not contain O--O, S--S, or S--O bonds. However,
one or more N or S atoms in a heteroaryl group can be oxidized
(e.g., pyridine N-oxide, thiophene S-oxide, thiophene S,S-dioxide).
Examples of heteroaryl groups include, for example, the 5-membered
monocyclic and 5-6 bicyclic ring systems shown below:
##STR00006## where T is O, S, NH, N-alkyl, N-aryl, or N-(arylalkyl)
(e.g., N-benzyl). Examples of such heteroaryl rings include
pyrrolyl, furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl,
pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl,
isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl,
oxadiazolyl, indolyl, isoindolyl, benzofuryl, benzothienyl,
quinolyl, 2-methylquinolyl, isoquinolyl, quinoxalyl, quinazolyl,
benzotriazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl,
benzisoxazolyl, benzoxadiazolyl, benzoxazolyl, cinnolinyl,
1H-indazolyl, 2H-indazolyl, indolizinyl, isobenzofuyl,
naphthyridinyl, phthalazinyl, pteridinyl, purinyl,
oxazolopyridinyl, thiazolopyridinyl, imidazopyridinyl,
furopyridinyl, thienopyridinyl, pyridopyrimidinyl, pyridopyrazinyl,
pyridopyridazinyl, thienothiazolyl, thienoxazolyl, thienoimidazolyl
groups, and the like. Further examples of heteroaryl groups include
4,5,6,7-tetrahydroindolyl, tetrahydroquinolinyl,
benzothienopyridinyl, benzofuropyridinyl groups, and the like. In
some embodiments, heteroaryl groups can be substituted as disclosed
herein.
As used herein, "solubilizing group" refers to a functional group
that makes the resultant molecule more soluble in most common
organic solvents than a hydrogen atom would if it occupied the same
position in a molecule (for the same molecule-solvent
combinations). Examples of solubilizing groups include, but are not
limited to alkyl (eg. methyl, ethyl, i-propyl, n-propyl, i-butyl,
s-butyl, n-butyl, hexyl, 2-methyl hexyl, octyl, 3,7-dimethyl octyl,
decyl, dodecyl, tetradecyl, hexadecyl), alkoxy (eg. methoxy,
ethoxy, i-propoxy, n-propoxy, i-butyloxy, s-butyloxy, n-butyloxy,
hexyloxy, 2-methyl hexyloxy, octyloxy, 3,7-dimethyl octyloxy,
decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy), thioalkyl (e.g
thiooctyl), alkylethers, thioethers.
The electron-donating or electron-withdrawing properties of several
hundred of the most common substituents, reflecting all common
classes of substituents have been determined, quantified, and
published. The most common quantification of electron-donating and
electronwithdrawing properties is in terms of Hammett .sigma.
values. Hydrogen has a Hammett .sigma. value of zero, while other
substituents have Hammett .sigma. values that increase positively
or negatively in direct relation to their electron-withdrawing or
electron-donating characteristics. Substituents with negative
Hammett .sigma. values are considered electron-donating, while
those with positive Hammett .sigma. values are considered
electron-withdrawing. See Lange's Handbook of Chemistry, 12th ed.,
McGraw Hill, 1979, Table 3-12, pp. 3-134 to 3-138, which lists
Hammett .sigma. values for a large number of commonly encountered
substituents and is incorporated by reference herein.
It should be understood that the term "electron-accepting group"
can be used synonymously herein with "electron acceptor" and
"electron-withdrawing group". In particular, an
"electron-withdrawing group" ("EWG") or an "electron-accepting
group" or an "electronacceptor" refers to a functional group that
draws electrons to itself more than a hydrogen atom would if it
occupied the same position in a molecule. Examples of electron
withdrawing groups include, but are not limited to, halogen or halo
(e.g., F, Cl, Br, I), --NO.sub.2, --CN, --NC,
--S(R.sup.0).sub.2.sup.+, --N(R.sup.0).sub.3.sup.+, --SO.sub.3H,
--SO.sub.2R.sup.0, --SO.sub.3R.sup.0, --SO.sub.2NHR.sup.0,
--SO.sub.2N(R.sup.0).sub.2, --COOH, --COR.sup.0, --COOR.sup.0,
--CONHR.sup.0, --CON(R.sup.0).sub.2, C.sub.1-40 haloalkyl groups,
C.sub.6-14 aryl groups, and 5-14 membered electronpoor heteroaryl
groups; where R.sup.0 is a C.sub.1-20 alkyl group, a C.sub.2-20
alkenyl group, a C.sub.2-20 alkynyl group, a C.sub.1-20 haloalkyl
group, a C.sub.1-20 alkoxy group, a C.sub.6-14 aryl group, a
C.sub.3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl
group, and a 5-14 membered heteroaryl group, each of which can be
optionally substituted as described herein. For example, each of
the C.sub.1-20 alkyl group, the C.sub.2-20 alkenyl group, the
C.sub.2-20 alkynyl group, the C.sub.1-20 haloalkyl group, the
C.sub.1-20 alkoxy group, the C.sub.6-14 aryl group, the C.sub.3-14
cycloalkyl group, the 3-14 membered cycloheteroalkyl group, and the
5-14 membered heteroaryl group can be optionally substituted with
1-5 small electron-withdrawing groups such as F, Cl, Br,
--NO.sub.2, --CN, --NC, --S(R.sup.0).sub.2.sup.+,
--N(R.sup.0).sub.3.sup.+, --SO.sub.3H, --SO.sub.2R.sup.0,
--SO.sub.3R.sup.0, --SO.sub.2NHR.sup.0, --SO.sub.2N(R.sup.0).sub.2,
--COOH, --COR.sup.0, --COOR.sup.0, --CONHR.sup.0,
--CON(R.sup.0).sub.2
It should be understood that the term "electron-donating group" can
be used synonymously herein with "electron donor". In particular,
an "electron-donating group" or an "electron-donor" refers to a
functional group that donates electrons to a neighboring atom more
than a hydrogen atom would if it occupied the same position in a
molecule. Examples of electron-donating groups include --OH,
--OR.sup.0, --NH2, --NHR.sup.0, --N(R.sup.0).sub.2, and 5-14
membered electron-rich heteroaryl groups, where R.sup.0 is a
C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.2-20
alkynyl group, a C.sub.6-14 aryl group, or a C.sub.3-14 cycloalkyl
group.
Various unsubstituted heteroaryl groups can be described as
electron-rich (or .pi.-excessive) or electron-poor (or
.pi.-deficient). Such classification is based on the average
electron density on each ring atom as compared to that of a carbon
atom in benzene. Examples of electron-rich systems include
5-membered heteroaryl groups having one heteroatom such as furan,
pyrrole, and thiophene; and their benzofused counterparts such as
benzofuran, benzopyrrole, and benzothiophene. Examples of
electron-poor systems include 6-membered heteroaryl groups having
one or more heteroatoms such as pyridine, pyrazine, pyridazine, and
pyrimidine; as well as their benzofused counterparts such as
quinoline, isoquinoline, quinoxaline, cinnoline, phthalazine,
naphthyridine, quinazoline, phenanthridine, acridine, and purine.
Mixed heteroaromatic rings can belong to either class depending on
the type, number, and position of the one or more heteroatom(s) in
the ring. See Katritzky, A. R and Lagowski, J. M., Heterocyclic
Chemistry (John Wiley & Sons, New York, 1960).
As used herein, "semicrystalline polymer" refers to a polymer that
has an inherent tendency to crystallize at least partially either
when cooled from the melt or deposited from solution, when
subjected to kinetically favorable conditions such as slow cooling,
or low solvent evaporation rate etc. The crystallization or lack
thereof can be readily identified by an expert in the field-of-art
by using several analytical methods, for eg. differential scanning
calorimetry (DSC) and/or X-ray diffraction (XRD).
As used herein, "annealing" refers to a post-deposition heat
treatment in to the semi-crystalline polymer film in ambient or
under reduced/increased pressure for a time duration of more than
100 seconds, and "annealing temperature" refers to the maximum
temperature that the polymer film is exposed to for at least 60
seconds during this process of annealing. Without wishing to be
bound by any particular theory, it is believed that annealing
results in an increase of crystallinity in the polymer film where
possible, thereby increasing field effect mobility. The increase in
crystallinity can be monitored by several methods, for eg. by
comparing the differential scanning calorimetry (DSC) or X-ray
diffraction (XRD) measurements of the as-deposited and the annealed
films.
At various places in the present specification, substituents of
compounds are disclosed in groups or in ranges. It is specifically
intended that the description include each and every individual
subcombination of the members of such groups and ranges. For
example, the term "C.sub.1-6 alkyl" is specifically intended to
individually disclose C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5,
C.sub.6, C.sub.1-C.sub.6, C.sub.1-C.sub.5, C.sub.1-C.sub.4,
C.sub.1-C.sub.3, C.sub.1-C.sub.2, C.sub.2-C.sub.6, C.sub.2-C.sub.5,
C.sub.2-C.sub.4, C.sub.2-C.sub.3, C.sub.3-C.sub.6, C.sub.3-C.sub.5,
C.sub.3-C.sub.4, C.sub.4-C.sub.6, C.sub.4-C.sub.5, and
C.sub.5-C.sub.6 alkyl. By way of other examples, an integer in the
range of 0 to 40 is specifically intended to individually disclose
0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,
36, 37, 38, 39, and 40, and an integer in the range of 1 to 20 is
specifically intended to individually disclose 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Additional
examples include that the phrase "optionally substituted with 1-5
substituents" is specifically intended to individually disclose a
chemical group that can include 0, 1, 2, 3, 4, 5, 0-5, 0-4, 0-3,
0-2, 0-1, 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, and 4-5
substituents.
Polymers described herein can contain an asymmetric atom (also
referred as a chiral center) and some of the compounds can contain
two or more asymmetric atoms or centers, which can thus give rise
to optical isomers (enantiomers) and diastereomers (geometric
isomers). The present teachings include such optical isomers and
diastereomers, including their respective resolved enantiomerically
or diastereomerically pure isomers (e.g., (+) or (-) stereoisomer)
and their racemic mixtures, as well as other mixtures of the
enantiomers and diastereomers. In some embodiments, optical isomers
can be obtained in enantiomerically enriched or pure form by
standard procedures known to those skilled in the art, which
include, for example, chiral separation, diastereomeric salt
formation, kinetic resolution, and asymmetric synthesis. The
present teachings also encompass cis- and trans-isomers of polymers
containing alkenyl moieties (e.g., alkenes, azo, and imines). It
also should be understood that the polymers of the present
teachings encompass all possible regioisomers in pure form and
mixtures thereof. It may be possible to separate such isomers, for
example, using standard separation procedures known to those
skilled in the art, for example, column chromatography, thin-layer
chromatography, simulated moving-bed chromatography, and
high-performance liquid chromatography. However, mixtures of
regioisomers can be used similarly to the uses of each individual
regioisomer of the present teachings. For example,
dithienylvinylene-based polymers of the present teachings can
include any geometrical isomer of the dithienylvinylene in its pure
form (eg. cis- and/or trans-) or mixtures thereof.
It is specifically contemplated that the depiction of one
regioisomer includes any other regioisomers and any regioisomeric
mixtures unless specifically stated otherwise.
Throughout the specification, structures may or may not be
presented with chemical names. Where any question arises as to
nomenclature, the structure prevails.
The present teachings provide A-B copolymers wherein the polymers
can be A-B copolymers of optionally substituted dithienylvinylenes
(monomer A) in conjugation with aromatic and/or heteroaromatic
cyclic moieties (monomer B). The present teachings provide A-B
copolymers, wherein monomer A is an optionally substituted
dithienylvinylene and monomer B is a .pi.-conjugated moiety
optionally functionalized with one or more electron withdrawing,
electron donating or solublizing groups. Monomer A and the cyclic
core pi-1 (.pi.-1) of monomer B are typically bonded to each other
via carbon atoms. Specifically, the polymers of the present
teachings have formula I:
##STR00007## or of the formula I':
##STR00008## wherein: pi-1, pi-2 are independently a monocyclic or
polycyclic moiety optionally substituted with 1-4 R.sup.8 groups;
wherein: R.sup.a, at each occurrence, is independently a) a
halogen, b) --CN, c) --NO.sub.2, d) oxo, e) --OH,
f).dbd.C(R.sup.b).sub.2; g) a C.sub.1-20 alkyl group, h) a
C.sub.2-20 alkenyl group, i) a C.sub.2-20 alkynyl group, j) a
C.sub.1-20 alkoxy group, k) a C.sub.1-20 alkylthio group, l) a
C.sub.1-20 haloalkyl group, m) --Y-a C.sub.3-10 cycloalkyl group,
n) --Y-a C.sub.6-14 aryl group, o) a --Y-3-12 membered
cycloheteroalkyl group, or p) a --Y-5-14 membered heteroaryl group,
wherein each of the C.sub.1-20 alkyl group, the C.sub.2-20 alkenyl
group, the C.sub.2-20 alkynyl group, the C.sub.3-10 cycloalkyl
group, the C.sub.6-14 aryl or haloaryl group, the 3-12 membered
cycloheteroalkyl group, and the 5-14 membered heteroaryl group is
optionally substituted with 1-4 R.sup.b groups; R.sup.b, at each
occurrence, is independently a) a halogen, b) --CN, c) --NO.sub.2,
d) oxo, e) --OH, f) --NH.sub.2, g) --NH(C.sub.1-20 alkyl),
h)--N(C.sub.1-20 alkyl).sub.2, i) --N(C.sub.1-20 alkyl)--C.sub.6-14
aryl, j) --N(C.sub.6-14 aryl).sub.2, k) --S(O).sub.mH, l)
--S(O).sub.m--C.sub.1-20 alkyl, m) --S(O).sub.2OH, n) --S(O).sub.m,
--OC.sub.1-20 alkyl, o) --S(O).sub.m, --OC.sub.6-14 aryl, p) --CHO,
q) --C(O)--C.sub.1-20 alkyl, r) --C(O)--C.sub.6-14 aryl, s)
--C(O)OH, t) --C(O)--OC.sub.1-20 alkyl, u) --C(O)--OC.sub.6-14
aryl, v) --C(O)NH.sub.2, w) --C(O)NH--C.sub.1-20 alkyl, x)
--C(O)N(C.sub.1-20 alkyl).sub.2, y) --C(O)NH--C.sub.6-14 aryl, z)
--C(O)N(C.sub.1-20 alkyl)--C.sub.6-14 aryl, aa) --C(O)N(C.sub.6-14
aryl).sub.2, ab) --C(S)NH.sub.2, ac) --C(S)NH--C.sub.1-20 alkyl,
ad) --C(S)N(C.sub.1-20 alkyl).sub.2, ae) --C(S)N(C.sub.6-14
aryl).sub.2, af) --C(S)N(C.sub.1-20 alkyl)--C.sub.6-14 aryl, ag)
--C(S)NH--C.sub.6-14 aryl, ah) --S(O).sub.mNH.sub.2, ai)
--S(O).sub.mNH(C.sub.1-20 alkyl), aj) --S(O).sub.mN(C.sub.1-20
alkyl).sub.2, ak) --S(O).sub.mNH(C.sub.6-14 aryl), al)
--S(O).sub.mN(C.sub.1-20 alkyl)--C.sub.6-14 aryl, am)
--S(O).sub.mN(C.sub.6-14 aryl).sub.2, an) SiH.sub.3, ao)
SiH(C.sub.1-20 alkyl).sub.2, ap) SiH.sub.2(C.sub.1-20 alkyl), ar)
--Si(C.sub.1-20 alkyl).sub.3, as) a C.sub.1-20 alkyl group, at) a
C.sub.2-20 alkenyl group, au) a C.sub.2-20 alkynyl group, av) a
C.sub.1-20 alkoxy group, aw) a C.sub.1-20 alkylthio group, ax) a
C.sub.1-20 haloalkyl group, ay) a C.sub.3-10 cycloalkyl group, az)
a C.sub.6-14 aryl or haloaryl group, ba) a 3-12 membered
cycloheteroalkyl group, or bb) a 5-14 membered heteroaryl group; Y,
at each occurrence, is independently a divalent C.sub.1-6 alkyl
group, a divalent C.sub.1-6 haloalkyl group, or a covalent bond;
and m, at each occurrence, is independently 0, 1 or 2;
R.sup.1, R.sup.2, at each occurrence, are independently H, halogen,
CN, a C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, a
C.sub.1-30 haloalkyl group, -L-Ar.sup.1, or
-L-Ar.sup.1--Ar.sup.1--R.sup.11; wherein: L, at each occurrence, is
independently --O--, --Y--O--Y, --S--, --S(O)--, --Y--S--Y--,
--C(O)--, --NR.sup.cC(O)--, --NR.sup.c--, --SiR.sup.c.sub.2--,
--Y--[SiR.sup.c.sub.2]--Y--, a divalent C.sub.1-30 alkyl group, a
divalent C.sub.1-30 alkenyl group, a divalent C.sub.1-30 haloalkyl
group, or a covalent bond; wherein: R.sup.c, at each occurrence, is
H, a C.sub.1-20 alkyl group, or a --Y--C.sub.6-14 aryl group;
Ar.sup.1, at each occurrence, is independently a C.sub.6-14 aryl
group or a 5-14 membered heteroaryl group, each optionally
substituted with 1-5 substituents selected from a halogen, --CN, a
C.sub.1-6 alkyl group, a C.sub.1-6 alkoxy group, and a C.sub.1-6
haloalkyl group; and R.sup.1, at each occurrence, is independently
a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.1-20
haloalkyl group, a C.sub.1-20 alkoxy group, -L'-Ar.sup.2,
-L-Ar.sup.2--Ar.sup.2, -L-Ar.sup.2--R.sup.12, or
-L-Ar.sup.2--Ar.sup.2--R.sup.12; wherein: L', at each occurrence,
is independently --O--, --Y--O--Y--, --S--, --S(O)--, --C(O)--,
--NR.sub.cC(O)--, --NR.sup.c--, --SiR.sup.c.sub.2,
--Y--[SiR.sup.c.sub.2]--Y--, a divalent C.sub.1-20 alkyl group, a
divalent C.sub.1-20 alkenyl group, a divalent C.sub.1-20 haloalkyl
group, or a covalent bond; Ar.sup.2, at each occurrence, is
independently a C.sub.6-14 aryl group or a 5-14 membered heteroaryl
group, each optionally substituted with 1-5 substituents selected
from a halogen, --CN, a C.sub.1-6 alkyl group, a C.sub.1-6 alkoxy
group, and a C.sub.1-6 haloalkyl group; and R.sup.12 at each
occurrence, is a C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl
group, a C.sub.1-20 haloalkyl group, or a C.sub.1-20 alkoxy
group;
R.sup.3, R.sup.4, at each occurrence, are independently H, CN, a
C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, a C.sub.1-30
haloalkyl group, or -L-R.sup.11; wherein: L, at each occurrence, is
independently --O--, Y--O--Y--, --S--, --S(O)--, --Y--S--Y--,
--C(O)--, --NR.sup.c'C(O)--, --NR.sup.c'--, a divalent C.sub.1-30
alkyl group, a divalent C.sub.1-30 alkenyl group, a divalent
C.sub.1-30 haloalkyl group, or a covalent bond; wherein: R.sup.c',
at each occurrence, is H, a C.sub.1-20 alkyl group, R.sup.11, at
each occurrence, is independently a C.sub.1-20 alkyl group, a
C.sub.2-20 alkenyl group, a C.sub.1-20 haloalkyl group;
Y, at each occurrence, is independently a divalent C.sub.1-6 alkyl
group, a divalent C.sub.1-6 haloalkyl group, or a covalent
bond;
y and y' at each occurrence are independently 0, 1 or 2 provided
that y+y'>0,
n is an integer greater than 1.
In some preferred embodiments, R.sup.1 and R.sup.2 are selected
from the group consisting of H, halogen, CN, a C.sub.1-30 alkyl
group, a C.sub.2-30 alkenyl group, a C.sub.1-30 haloalkyl group, a
C.sub.1-20 alkoxy group, and a C.sub.1-20 alkylthio group.
In some preferred embodiments, R.sup.3 and R.sup.4 are selected
from the group consisting of R.sup.3, R.sup.4, at each occurrence,
are independently H, CN, halogen, a C.sub.1-30 alkyl group, a
C.sub.2-30 alkenyl group, a C.sub.1-30 haloalkyl group, a
C.sub.1-20 alkoxy group and a C.sub.1-20 alkylthio group.
In a preferred embodiment the polymers of the present teachings can
have the formula I as defined above with the proviso that if
y+y'=1, and if R.sup.3.dbd.R.sup.4.dbd.H, neither pi-1 nor pi-2 is
unsubstituted, N-monosubstituted or N,N'-disubstituted
1,4,5,8-naphthalene diimide-2,6-diyl or is unsubstituted or
N-monosubstituted 1,8-naphthalene monoimide-2,6-diyl or is
monosubstituted or N,N'-disubstituted 1,4,5,8-naphthalene
diimide-2,7-diyl or is unsubstituted or N-monosubstituted
1,8-naphthalene monoimide-3,6-diyl or is unsubstituted;
N-monosubstituted or N,N'-disubstituted
3,4,9,10-perylenediimide-1,7-diyl or is unsubstituted,
N-monosubstituted or N,N'-disubstituted
3,4,9,10-perylenediimide-1,6-diyl or is unsubstituted or
N-monosubstituted and/or 9,10 disubstituted 3,4-perylene
monoimide-1,7-diyl or is unsubstituted or N-monosubstituted and/or
9,10 disubstituted 3,4-perylene monoimide-1,6-diyl.
Furthermore, to aid solubility and without causing disruption of
the intrachain .pi.-conjugation and interchain stacking, alkyl
chains (and similar groups such as haloalkyl groups, arylalkyl
groups, heteroarylalkyl groups and so forth) can be substituted
symmetrically on one or both positions of the thiophene rings
and/or on the vinyl linkage. Accordingly, in certain preferred
embodiments, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 can
independently be a linear or branched C.sub.1-20 alkyl group or a
linear or branched C.sub.2-20 alkenyl group. For example, R.sup.1,
R.sup.2, R.sup.3, R.sup.4 at each occurrence independently can be
selected from n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl
and n-hexadecyl. In certain embodiments, at least one of R.sup.1
and R.sup.2 can be H.
In some embodiments, pi-1 and pi-2 can independently be a planar
and highly conjugated cyclic core, wherein the ring atoms are
covalently bonded with alternating single and double bonds. The
highly conjugated and planar nature of such cores can promote
.pi.-electron delocalization (thereby increasing stability and
lowering LUMO energy), and provide good intermolecular n-stacking.
Examples of suitable cyclic cores include benzene, naphthalene,
anthracene, tetracene, pentacene, perylene, pyrene, coronene,
fluorene, indacene, indenofluorene, and tetraphenylene, as well as
their analogs in which one or more carbon atoms are replaced with a
heteroatom such as O, S, Si, Se, N or P.
In some embodiments, pi-1 can be an optionally substituted
monocyclic, bicyclic or heterocyclic moiety selected from:
##STR00009## wherein: k, I, p, p' and u independently are selected
from --S--, --O--, --CH.dbd., .dbd.CH.dbd., --CR.sup.13.dbd.,
.dbd.CR.sup.13--, --C(O)--, --C(C(CN).sub.2)--, --N.dbd., .dbd.N--,
--NH-- and --NR.sup.13 and pi-2 can be an optionally substituted
monocyclic, heterocyclic or polycyclic moiety selected from:
##STR00010## ##STR00011## wherein: k, k', l, l', p, p', q, u, u', v
and v' independently are selected from --S--, --O--, --CH.dbd.,
.dbd.CH--, --CR.sup.13.dbd., .dbd.CR.sup.13--, --C(O)--,
--C(C(CN).sub.2)--, --N.dbd., .dbd.N--, --NH--, --NR.sup.13--,
--SiR.sup.14.dbd., .dbd.SiR.sup.14--, and --SiR.sup.14R.sup.14--;
R.sup.13, at each occurrence, is independently selected from a)
halogen, b) --CN, c) --NO.sub.2, d) N(R.sup.c).sub.2, e)
--OR.sup.c, f) --C(O)R.sup.c, g) --C(O)OR.sup.c, h)
--C(O)N(R.sup.c, i) a C.sub.1-40 alkyl group, j) a C.sub.2-40
alkenyl group, k) a C.sub.2-40 alkynyl group, l) a C.sub.1-40
alkoxy group, m) a C.sub.1-40 alkylthio group, n) a C.sub.1-40
haloalkyl group, o) a --Y--C.sub.3-14 cycloalkyl group, p) a
--Y--C.sub.6-14 aryl group, q) a --Y-3-14 membered cycloheteroalkyl
group, and r) a --Y-5-14 membered heteroaryl group, wherein each of
the C.sub.1-40 alkyl group, the C.sub.2-40 alkenyl group, the
C.sub.2-40 alkynyl group, the C.sub.3-14 cycloalkyl group, the
C.sub.6-14 aryl group, and the 3-14 membered cycloheteroalkyl group
and Y and R.sup.c are as defined herein. R.sup.14, at each
occurrence, independently can be H or R.sup.c, wherein R.sup.c is
as defined herein; r and s independently can be --CR.sup.2R.sup.2--
or --C(C(CN).sub.2)--; and b is 1, 2, 3 or 4.
In certain embodiments be pi-1 (.pi.-1) can be monocyclic, bicyclic
or heterocyclic moiety including one or more thienyl, thiazolyl, or
phenyl groups, where each of these groups can be optionally
substituted as disclosed herein. For example, pi-1 can be selected
from
##STR00012## wherein R.sup.1 and R.sup.2 at each occurrence are as
defined herein.
In certain embodiments pi-2 (.pi.-2) can be monocyclic, polycyclic
or heterocyclic moiety including one or more thienyl, thiazolyl, or
phenyl groups, where each of these groups can be optionally
substituted as disclosed herein. For example, pi-2 can be selected
from
##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017##
##STR00018## wherein R.sup.1 and R.sup.2 at each occurrence are as
defined herein.
In some preferred embodiments, y=0 and pi-2 is selected from the
group consisting of
##STR00019##
It should be understood that the present teachings can exclude
certain embodiments of compounds within the genus of compounds of
formula I described above. For example, it should be understood
that embodiments of the present teachings can exclude a polymer of
formula I wherein comonomer B is one monocyclic unit. As an
example, embodiments of the present teachings can exclude a polymer
of formula I wherein monomer B is
##STR00020##
As a further example, it should be understood that embodiments of
the present teachings can exclude a polymer of formula I wherein
comonomer B is a bicyclic or tricyclic unit without a nitrogen atom
and without a sulfur atom in the cyclic moiety. As an example,
embodiments of the present teachings can exclude a polymer of
formula I wherein monomer B is
##STR00021##
As a further example, it should be understood that embodiments of
the present teachings can exclude a polymer of formula I, wherein
comonomer B consists of a benzathiazole moiety. In particular,
embodiments of the present teachings can exclude a polymer of
formula I wherein B is
##STR00022##
For the various polymers described above, n can be an integer
between 2 and 5000. In some embodiments, n can be 4-5000, 5-5000,
6-5000, 7-5000, 8-5000, 9-5000, or 10-5000. For example, n can be
8-4000, 8-2000, 8-500, or 8-200. In certain embodiments, n can be
8-100.
Accordingly, in certain embodiments, the polymers of present
teaching can include repeating units of Formula Ia or Ia'
##STR00023## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are as
defined herein, R.sup.5 and R.sup.6 are defined as R.sup.1, and m''
is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
For example in certain embodiments, polymers of the present
teaching can include repeating units of one or more of Formulae Ib,
Ic, Id, Ie, If, Ig, Ih, Ii, and Ij
##STR00024## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.5 are as
defined herein. For example, R.sup.3 at each occurrence, can be
independently selected from --CN, a C.sub.1-40 alkyl group,
C.sub.1-40 alkoxy group and C.sub.1-40 alkylthiol group.
As a further example, certain embodiments of the polymers of the
present teachings can include repeating units of one or more of
Formulae Ik, Il, Im, In, Io, Ip, Iq, Ir, Is, It, Iu, Iv, Iw, Ix,
Iy, Iz, Iaa, Iab and Iac:
##STR00025## ##STR00026## ##STR00027## wherein R.sup.1, R.sup.2,
R.sup.3, R.sup.5 and R.sup.6 are as defined herein. R.sup.7 is
defined as R.sup.1. For example, R.sup.3 at each occurrence, can be
independently selected from --CN, a C.sub.1-30 alkyl group,
C.sub.1-20 alkoxy group and C.sub.1-20 alkylthiol group.
As a further example, certain embodiments of the polymers of the
present teaching include repeating units of the formula lad:
##STR00028## wherein R.sup.5 is as defined herein.
As a still further example, certain embodiments of the polymers of
the present teaching include repeating units of the formula Iae and
Iaf:
##STR00029## wherein R.sup.1 and R.sup.2 are as defined herein.
As a still further example, certain embodiments of the polymers of
the present teaching include repeating units of the formula Iag,
Iah, Ial, Iak and Ial
##STR00030## ##STR00031## wherein R.sup.1, R.sup.2 and R.sup.3 are
as defined herein.
Further, in certain embodiments, the polymers of present teaching
can include repeating units of Formulae IIa and IIa'
##STR00032## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and
R.sup.7 are as defined herein,
R.sup.8 is defined as R.sup.1,
R.sup.9 and R.sup.10 can be independently selected from --H or a
C.sub.1-40 alkyl, haloalkyl or alkylthiol group. For example,
R.sup.3 at each occurrence, can be independently selected from
--CN, a C.sub.1-30 alkyl group, C.sub.1-20 alkoxy group and
C.sub.1-20 alkylthiol group.
and m is 1, 2, 3, 4, 5 or 6.
For example in certain embodiments, polymers of the present
teaching can include repeating units of one or more of Formulae
IIb, IIc, IId, IIe, IIf and IIg.
##STR00033## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.9 and
R.sup.10 are as defined herein. For example, R.sup.3 at each
occurrence, can be independently selected from --CN, a C.sub.1-30
alkyl group, C.sub.1-20 alkoxy group and C.sub.1-20 alkylthiol
group.
As a further example, in certain embodiments, polymers of the
present teaching can include repeating units of one or more of
Formulae IIb', IIc', IId', IIe', IIf', IIg', IIh', IIi', IIj',
IIk', IIl', IIm', IIn', IIo' and IIp'.
##STR00034## ##STR00035## ##STR00036## wherein R.sup.1, R.sup.2,
R.sup.3, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are as defined
herein.
Further, in certain embodiments, the polymers of present teaching
can include repeating units of Formulae IIIa and IIIa'
##STR00037## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and m are as defined herein.
For example in certain embodiments, polymers of the present
teaching can include repeating units of one or more of Formulae
IIIb, IIIc, IIId, IIIe, IIIf and IIIg.
##STR00038## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.5 are as
defined herein. For example, R.sup.3 at each occurrence, can be
independently selected from --CN, a C.sub.1-30 alkyl group,
C.sub.1-20 alkoxy group and C.sub.1-20 alkylthiol group.
As a further example, in certain embodiments, polymers of the
present teaching can include repeating units of one or more of
Formulae IIIb', IIIc', IIId', IIIe', IIIf', IIIg', IIIh', IIIi',
IIIj', IIIk', IIIl', IIIm', IIIn', IIIo' and IIIp'.
##STR00039## ##STR00040## ##STR00041## wherein R.sup.1, R.sup.2,
R.sup.3, R.sup.5, R.sup.2 and R.sup.8 are as defined herein. For
example, R.sup.3 at each occurrence, can be independently selected
from --CN, halogen, a C.sub.1-20 haloalkyl group, a C.sub.1-30
alkyl group, C.sub.1-20 alkoxy group and C.sub.1-20 alkylthiol
group.
Certain embodiments of the present polymers can be prepared in
accordance with the procedures outlined in Scheme 1 below:
##STR00042##
Referring to Scheme 1, certain embodiments of the present polymers
can be synthesized via a metal catalyzed Stille polymerization. In
particular, an acyl chloride can be reacted with
alkyl-bromothiophene under Friedel-Craft's reaction conditions to
yield the monobromo-keto derivative of thiophene (TK-Br). McMurray
homocoupling of the TK-Br provides the desired monomer TVT-Br2.
Polymerization of TVT-Br2 with the appropriate organotin compound
in the presence of metal catalyst such as
Tris(dibenzylideneacetone)dipalladium(0) Pd.sub.2(dba).sub.3 leads
to the desired polymer. Endcapping of the polymer chains can be
done by addition of 1-10% monobromo or mono(trialkylstannyl)
aromatic or heteroaromatic units before workup of the
polymerization mixture.
Scheme 2 below shows an alternative synthesis for preparing certain
embodiments of the present polymers:
##STR00043##
Other polymers of the present teachings can be prepared in
accordance with the procedures analogous to those described in
Schemes 1 and 2. Alternatively, the present polymers can be
prepared from commercially available starting materials, compounds
known in the literature, or readily prepared intermediates, by
employing standard synthetic methods and procedures known to those
skilled in the art. Standard synthetic methods and procedures for
the preparation of organic molecules and functional group
transformations and manipulations can be readily obtained from the
relevant scientific literature or from standard textbooks in the
field. It will be appreciated that where typical or preferred
process conditions (i.e., reaction temperatures, times, mole ratios
of reactants, solvents, pressures, etc.) are given, other process
conditions can also be used unless otherwise stated. Optimum
reaction conditions can vary with the particular reactants or
solvent used, but such conditions can be determined by one skilled
in the art by routine optimization procedures. Those skilled in the
art of organic synthesis will recognize that the nature and order
of the synthetic steps presented can be varied for the purpose of
optimizing the formation of the compounds described herein.
The processes described herein can be monitored according to any
suitable method known in the art. For example, product formation
can be monitored by spectroscopic means, such as nuclear magnetic
resonance spectroscopy (NMR, e.g., .sup.1H or .sup.13C), infrared
spectroscopy (IR), spectrophotometry (e.g., UV-visible), mass
spectrometry (MS), or by chromatography such as high pressure
liquid chromatograpy (HPLC), gas chromatography (GC),
gel-permeation chromatography (GPC), or thin layer chromatography
(TLC).
The reactions or the processes described herein can be carried out
in suitable solvents which can be readily selected by one skilled
in the art of organic synthesis. Suitable solvents typically are
substantially nonreactive with the reactants, intermediates, and/or
products at the temperatures at which the reactions are carried
out, i.e., temperatures that can range from the solvent's freezing
temperature to the solvent's boiling temperature. A given reaction
can be carried out in one solvent or a mixture of more than one
solvent. Depending on the particular reaction step, suitable
solvents for a particular reaction step can be selected.
Exemplary polymers from the present teachings include P(TS8TVT)
(P1), P(BDT12TVT) (P2), P(T2-14-TVT) (P3), and P(T2-12-TVT) (P4),
the structures of which are shown below.
##STR00044##
Without limiting the scope of present teachings in anyway and only
for the purpose of illustration, certain embodiments of the
polymers of the present teachings can be characterized by one and
more of the physical properties described herein below. Further,
for the purpose of comparison two bithiophene containing copolymers
may be discussed along with the polymers of the present teachings.
The structures of the two bithiophene containing copolymers are as
follows:
##STR00045##
The molecular weights of the polymers of the present teachings can
be determined using size exclusion chromatography (SEC). In an
embodiment of polymer of Formula Ib where R5 is C.sub.12H.sub.25
specifically P4, its molecular weight (M.sub.n) was determined by
SEC to be 1.6.times.10.sup.4 g/mol. Its polydispersity index (PDI)
was determined to be 2.2. For another embodiment of polymer of
Formula Ib where R5 is C.sub.14H.sub.29, specifically P3, its
molecular weight (M.sub.n) was determined by SEC to be
1.7.times.10.sup.4 g/mol. Its polydispersity index (PDI) was
determined to be 1.8. Similarly, for an embodiment of polymer of
Formula IIb where R9 and R10 are C.sub.8H.sub.17, specifically P1,
its molecular weight (M.sub.n) was determined by SEC to be
4.1.times.10.sup.4 g/mol. Its polydispersity index (PDI) was
determined to be 5.6. Similarly, for an embodiment of polymer of
Formula IIIb where R5 is C.sub.12H.sub.25, specifically P2, its
molecular weight (M.sub.n) was determined by SEC to be
2.5.times.10.sup.4 g/mol. Its polydispersity index (PDI) was
determined to be 1.4. Polymer P6 with C.sub.8H.sub.17 alkyl chain
was also synthesized for comparision and its molecular weight
(M.sub.n) was determined by SEC to be 1.05.times.10.sup.5 g/mol.
Its polydispersity index (PDI) was determined to be 4.0.
Thermal properties of the polymers of the present teachings can
also be examined by differential scanning calorimetry (DSC). For
example, using a scanning speed of 10.degree. C./min. under
nitrogen, it was observed that an embodiment of polymer P4
exhibited an endothermic transition at 117.degree. C. on heating
and exothermic transitions at 77.degree. C. and 124.degree. C. on
cooling, while an embodiment of polymer P3 exhibited an endothermic
transition at 106.degree. C. on heating and exothermic transitions
at 66.degree. C., 90.degree. C. on cooling. Polymer P1 showed an
endothermic transition at 256.degree. C. on heating cycle, while P2
demonstrated an endothermic transition at 179.degree. C. on
heating, but these polymers did not show any exothermic transitions
on the cooling cycle. Polymer P6 exhibited an endothermic
transition at 247.degree. C. on heating and exothermic transition
at 241.degree. C. on cooling.
Polymers of formula I can be used to prepare semiconductor
materials (e.g., compositions and composites), which in turn can be
used to fabricate various articles of manufacture, structures and
devices. In some embodiments, semiconductor materials incorporating
one or more polymers of the present teachings can exhibit n-type
semiconducting activity and in some embodiments, semiconductor
materials incorporating one or more polymers of the present
teachings can exhibit p-type semiconducting activity.
Given their relatively high solubilities in common solvents, the
compounds of the present teachings can offer processing advantages
when used to fabricate electrical devices such as thin film
semiconductors, field-effect devices, organic light emitting diodes
(OLEDs), organic photovoltaics, photodetectors, capacitors, and
sensors. As used herein, a compound can be considered soluble in a
solvent when at least 0.1 mg of the compound is soluble in 1 mL of
the solvent. Examples of common organic solvents include petroleum
ethers; acetonitrile; aromatic hydrocarbons such as benzene,
toluene, xylene, and mesitylene; ketones, such as acetone, and
methyl ethyl ketone; ethers, such as tetrahydrofuran, dioxane,
bis(2-methoxyethyl)ether, diethyl ether, diisopropyl ether, and
t-butyl methyl ether; alcohols, such as methanol, ethanol, butanol,
and isopropyl alcohol; aliphatic hydrocarbons, such as hexanes;
acetates, such as methyl acetate, ethyl acetate, methyl formate,
ethyl formate, isopropyl acetate, and butyl acetate; halogenated
aliphatic and aromatic hydrocarbons, such as dichloromethane,
chloroform, ethylene chloride, chlorobenzene, dichlorobenzene, and
trichlorobenzene; and cyclic solvents such as cyclopentanone,
cyclohexanone, and 2-methypyrrolidone.
Various deposition techniques, including various
solution-processing techniques, have been used with organic
electronics. For example, much of the printed electronics
technology has focused on inkjet printing, primarily because this
technique offers greater control over feature position and
multilayer registration. Inkjet printing is a noncontact process,
which offers the benefits of not requiring a preformed master
(compared to contact printing techniques), as well as digital
control of ink ejection, thereby providing drop-on-demand printing.
However, contact printing techniques have the key advantage of
being well-suited for very fast roll-to-roll processing. Exemplary
contact printing techniques include screen-printing, gravure,
offset, flexo, and microcontact printing. Other solution processing
techniques include, for example, spin coating, drop-casting, zone
casting, dip coating, and blade coating.
The present polymers can exhibit versatility in their processing.
Formulations including the present polymers can be printable via
different types of printing techniques including gravure printing,
flexographic printing, and inkjet printing, providing smooth and
uniform films that allow, for example, the formation of a
pinhole-free dielectric film thereon, and consequently, the
fabrication of all-printed devices.
The present teachings, therefore, further provide methods of
preparing a semi-conductor material. The methods can include
preparing a composition that includes one or more polymers
disclosed herein dissolved or dispersed in a liquid medium such as
a solvent or a mixture of solvents, depositing the composition on a
substrate to provide a semiconductor material precursor, and
processing (e.g., heating) the semi-conductor precursor to provide
a semiconductor material (e.g., a thin film semiconductor) that
includes a polymer disclosed herein. In some embodiments, the
depositing step can be carried out by printing, including inkjet
printing and various contact printing techniques (e.g.,
screen-printing, gravure, offset, pad, and microcontact printing).
In other embodiments, the depositing step can be carried out by
vacuum vapor deposition, spin coating, drop-casting, zone casting,
dip coating, blade coating, or spraying.
The present teachings further provide articles of manufacture, for
example, composites that include a semiconductor material of the
present teachings and a substrate component and/or a dielectric
component. The substrate component can be selected from materials
including doped silicon, an indium tin oxide (ITO), ITO-coated
glass, ITO-coated polyimide or other plastics, aluminum or other
metals alone or coated on a polymer or other substrate, a doped
polythiophene, and the like. The dielectric component can be
prepared from inorganic dielectric materials such as various oxides
(e.g., SiO.sub.2, Al.sub.2O.sub.3, HfO.sub.2), organic dielectric
materials such as various polymeric materials (e.g., the
crosslinked polymer blends described in U.S. patent application
Ser. Nos. 11/315,076, 60/816,952, and 60/861,308, the entire
disclosure of each of which is incorporated by reference herein)
and a self-assembled superlattice/self-assembled nanodielectric
(SAS/SAND) material (described in Yoon, M-H. et al., PNAS, 102
(13): 4678-4682 (2005), the entire disclosure of which is
incorporated by reference herein), as well as a hybrid
organic/inorganic dielectric material (described in U.S. patent
application Ser. No. 11/642,504, the entire disclosure of which is
incorporated by reference herein). The composite also can include
one or more electrical contacts. Suitable materials for the source,
drain, and gate electrodes include metals (e.g., Au, Al, Ni, Cu),
transparent conducting oxides (e.g., ITO, IZO, ZITO, GZO, GIO,
GITO), and conducting polymers (e.g.,
poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
(PEDOT:PSS), polyaniline (PANI), polypyrrole (PPy)). One or more of
the composites described herein can be embodied within various
organic electronic, optical, and optoelectronic devices such as
organic thin film transistors (OTFTs), specifically, organic field
effect transistors (OFETs), as well as sensors, solar cells,
capacitors, complementary circuits (e.g., inverter circuits), and
the like.
Accordingly, an aspect of the present teachings relates to methods
of fabricating an organic field effect transistor that incorporates
a semiconductor material of the present teachings. The
semiconductor materials of the present teachings can be used to
fabricate various types of organic field effect transistors
including top-gate top-contact capacitor structures, top-gate
bottom-contact capacitor structures, bottom-gate top-contact
capacitor structures, and bottomgate bottom-contact capacitor
structures. FIG. 3 illustrates the four common types of OFET
structures: (a) bottom-gate top-contact structure, (b) bottom-gate
bottom-contact structure, (c) top-gate bottom-contact structure,
and (d) top-gate top-contact structure. As shown in FIG. 3, an OFET
can include a dielectric layer (e.g., shown as 8, 8', 8'', and 8'''
in FIGS. 3a, 3b, 3c, and 3d, respectively), a semiconductor layer
(e.g., shown as 6, 6', 6'', and 6''' in FIGS. 3a, 3b, 3c, and 3d,
respectively), a gate contact (e.g., shown as 10, 10', 10'', and
10''' in FIGS. 3a, 3b, 3c, and 3d, respectively), a substrate
(e.g., shown as 12, 12', 12'', and 12''' in FIGS. 3a, 3b, 3c, and
3d, respectively), and source and drain contacts (e.g., shown as 2,
2', 2'', 2''', 4, 4', 4'', and 4''' in FIGS. 3a, 3b, 3c, and 3d,
respectively).
Another article of manufacture in which the polymers of the present
teachings are useful is photovoltaics or solar cells. The polymers
of the present teachings can exhibit broad optical absorption.
Accordingly, depending on nature of the comonomer B unit, the
polymers described herein can be used as an n-type or p-type
semiconductor in a photovoltaic design, which includes an adjacent
p-type or n-type semiconducting material respectively to form a p-n
junction. The polymers can be in the form of a thin film
semiconductor, which can be a composite of the thin film
semiconductor deposited on a substrate. Exploitation of the
polymers of the present teachings in such devices is within the
knowledge of the skilled artisan.
Accordingly, another aspect of the present teachings relates to
methods of fabricating an organic field effect transistor that
incorporates a semiconductor material of the present teachings. The
semiconductor materials of the present teachings can be used to
fabricate various types of organic field effect transistors
including top-gate top-contact capacitor structures, top-gate
bottom-contact capacitor structures, bottom-gate top-contact
capacitor structures, and bottom-gate bottom-contact capacitor
structures.
In certain embodiments, OTFT devices can be fabricated with the
present compounds on doped silicon substrates, using SiO.sub.2 as
the dielectric, in top-contact geometries. In particular
embodiments, the active semiconducting layer which incorporates at
least a compound of the present teachings can be applied by
spin-coating or jet printing. For top-contact devices, metallic
contacts can be patterned on top of the films using shadow
masks.
In certain embodiments, OTFT devices can be fabricated with the
present polymers on plastic foils, using polymers as the
dielectric, in top-gate bottom-contact geometries. In particular
embodiments, the active semiconducting layer which incorporates at
least a polymer of the present teachings can be deposited at room
temperature or at an elevated temperature. In other embodiments,
the active semiconducting layer which incorporates at least a
polymer of the present teachings can be applied by spin-coating or
printing as described herein. Gate and source/drain contacts can be
made of Au, other metals, or conducting polymers and deposited by
vapor-deposition and/or printing.
The following examples are provided to illustrate further and to
facilitate the understanding of the present teachings and are not
in any way intended to limit the invention.
EXAMPLE 1
Polymer Synthesis
The following examples describe the preparation of certain polymers
of the present teaching and related intermediates
All reagents were purchased from commercial sources and used
without further purification unless otherwise noted. Conventional
Schlenk techniques were used, and reactions were carried out under
N2 unless otherwise noted. NMR spectra were recorded on a Varian
400MR spectrometer (.sup.1H, 400 MHz). Polymer molecular weights
were determined on Agilent 1200 series with refractive index
detector in THF at room temperature versus polystyrene standards.
The thermal characteristics of polymer were studied using a
differential scanning calorimeter (DSC) (Mettler Toledo,
DSC/823e/500/404) with a scanning rate of 10.degree. C./min.
Elemental analyses were performed at the National University of
Singapore. 5,5'-dibromo-4,4'-bi(dodecyl)-2,2'-bithiophene
(McCulloch, I.; Heeney, M.; Genevicius, K.; MacDonald, I.; Shkunov,
M.; Sparrowe, D.; Tierney, S.; Wagner, R.; Zhang, W.; Chabinyc, M.
L.; Kline, R. J.: McGehee, M. D.; Toney, F. M. Nat. Mater. 2006, 5,
328), 3,3'-dibromo-2,2'-bithiophene (Lu, G.; Usta, H.; Risko, C.;
Wang, L.; Facchetti, A.; Ratner, M. A.; Marks, T. J. J. Am. Chem.
Soc. 2008, 130, 7670-7685) and
2,6-Dibromo-4,8-didodecylbenzo[1,2-b:4,5-b']dithiophene (H. Pan, Y.
Li, Y. Wu, P. Liu, B. S. Ong, S. Zhu, G. Xu, Chem. Mater. 2006, 18,
3237) were prepared according to literature procedures.
EXAMPLE 1A
Preparation of poly
[(1,2-bis-(2'-thienyl)vinyl-5',5''-diyl)-alt-(3,3'-di-n-octylsilylene-2,2-
'-bithiophene-5,5'-diyl)]
Preparation of
5,5'-bis(trimethylstannyl)[1,2-bis(2'-thienyl)vinyl]
##STR00046##
Trans-1,2-di(2-thienyl)ethylene (1) (10.4 mmol, 2.00 g) was
dissolved in anhydrous THF (43.2 mL) and cooled to -78.degree. C.
under nitrogen. n-Butyllithium (21.84 mmol, 13.7 mL) was then added
dropwise. The resulting solution was warmed to room temperature
over 30 min and stirred at that temperature for 3 h. The mixture
was then cooled to -78.degree. C. before trimethyltin chloride
(21.84 mmol, 4.35 g) in anhydrous THF (26 mL) was added dropwise.
After addition, the mixture was warmed to room temperature over 4 h
and stirred for additional 20 h at room temperature. The reaction
mixture was poured into saturated NH.sub.4Cl solution (100 mL) and
the aqueous layer was extracted with diethyl ether. The combined
organic layers were washed with water, dried over Na.sub.2SO.sub.4
and concentrated under reduced pressure. The crude solid was
recrystallized from ethanol to give desired compound 2 in 73%
yield. .sup.1H-NMR (CDCl.sub.3) (400 MHz) ppm 7.12 (d, 2H) ppm 7.09
(s, 2H) ppm 7.07 (d, 2H) ppm 0.38 (s, 18H).
Preparation of 3,3'-di-n-octylsilylene-2,2'-bithiophene
##STR00047##
To a solution of n-BuLi in hexane (60 mmol, 24 mL) in anhydrous THF
(500 mL) at -78.degree. C. was added dropwise under vigorous
stirring a solution of 3,3'-dibromo-2,2'-bithiophene (3) (30 mmol,
9.720 g) in anhydrous THF (100 mL) over 30 min. The mixture was
then stirred at -78.degree. C. for 1 h, resulting in a white
suspension. Next, a solution of dichlorodioctylsilane (30 mmol,
9.76 g) in THF (100 mL) was added dropwise. The reaction mixture
was stirred at -78.degree. C. for five additional hours, allowed to
warm to room temperature, and stirred overnight. The reaction was
next quenched by adding saturated aqueous NH.sub.4Cl solution (300
mL). The aqueous layer was extracted with ether (3.times.100 mL).
The organic phases were then combined and washed with water and
dried over MgSO.sub.4. After filtration, the solvent was removed,
and the crude product was purifled by column chromatography to
yield a light yellow liquid 4 (8.17 g, 65%). .sup.1H NMR
(CDCl.sub.3): ppm 0.85-0.93 (m, 10H), ppm 1.24-1.41 (m, 24H), ppm
7.06 (d, 2H, J=5 Hz), ppm 7.21 (d, 2H, J=5 Hz).
Preparation of
5,5'-dibromo-3,3'-di-n-octylsilylene-2,2'-bithiophene
##STR00048##
To a solution of 3,3'-di-n-octylsilylene-2,2'-bithiophene (4) (1.63
g, 5.0 mmol) in DMF (40 mL) was added NBS (1.98 g, 11.0 mmol) in
many portion. The mixture was stirred at room temperature for 10
min, and then water (50 mL) was added to quench the reaction. The
reaction mixture was extracted with ether (3.times.50 mL). The
combined organic phase was washed with water (50 mL) and dried over
MgSO.sub.4. After filtration, the ether was removed, and the
product was purified by column chromatography using hexane as
eluent to give a green liquid 5 (2.05 g, 71%). .sup.1H NMR
(CDCl.sub.3): ppm 0.86-0.88 (m, 10H), ppm 1.32-1.22 (m, 24 H), ppm
7.00 (s, 2H).
Preparation of poly
[(1,2-bis-(2'-thienyl)vinyl-5',5''-diyl)-alt-(3,3'-di-n-octylsilylene-2,2-
'-bithiophene-5,5'-diyl)] (Polymer P1)
##STR00049##
Equimolar amounts of
bis(trimethylstannyl)trans-1,2-di(2-thienyl)ethylene (2) (0.50
mmol, 0.26 g) and dibromo monomer 5 (0.50 mmol, 0.29 g) were
dissolved in anhydrous toluene (10.0 mL) followed by the addition
of tetrakis(triphenylphosphine)palladium(0) (0.025 mmol, 29 mg)
under N2. The resulting mixture was refluxed for 2 days under
N.sub.2. Thereafter, 2-(trimethylstannyl)thiophene (0.2 mL) and
2-bromo-thiophene (0.2 mL) were added to endcap the polymer at the
interval of 3 hours and the reaction mixture was refluxed for an
additional 6 hours. After being cooled to room temperature, the
reaction mixture was precipitated into a mixture of methanol (300
mL) and stirred for 2 h at room temperature. The polymer P1 was
filtered, washed with methanol and subjected to Soxhlet extraction
for 24 h in acetone. The polymer P1 was redissolved in toluene and
precipitated from methanol, filtered, washed with methanol and
dried. Mn=4.1.times.10.sup.4 g/mol, Mw=2.3.times.10.sup.5 g/mol,
D=5.6.
.sup.1H-NMR (THF-d.sub.a) (400 MHz) ppm 7.28-7.05 (m, 8H) ppm
1.54-1.16 (m, 24H) ppm 1.02 (m, 4H) ppm 0.87 (t, 6H, J=6.6 Hz).
Elemental analysis (calcd): C, 66.88 (67.27); H, 6.69 (6.97).
EXAMPLE 1B
Preparation of poly
[(1,2-bis-(2'-thienyl)vinyl-5',5''-diyl)-alt-(4,8-didodecylbenzo-[1,2-b:4-
,5-b']-dithiophene-2,6-diyl)] (Polymer P2).
##STR00050##
Equimolar amounts of
bis(trimethylstannyl)trans-1,2-di(2-thienyl)ethylene (2) (0.29
mmol, 0.15 g) and dibromo monomer 6 (0.29 mmol, 0.20 g) were
dissolved in anhydrous chlorobenzene (10.0 mL) followed by the
addition of tri(dibenzylideneacetone)dipalladium(0) (0.009 mmol, 8
mg) and tri(o-tolyl)phosphine (0.022 mmol, 6 mg) under N.sub.2. The
resulting mixture was refluxed for 2 days under N.sub.2.
Thereafter, 2-(trimethylstannyl)thiophene (0.1 mL) and
2-bromo-thiophene (0.1 mL) were added to endcap the polymer at the
interval of 3 hours and the reaction mixture was refluxed for an
additional 6 hours. After being cooled to room temperature, the
reaction mixture was precipitated into a mixture of methanol (300
mL) and hydrochloric acid (10 mL, 2N) and stirred for 2 h at room
temperature. The polymer P2 was filtered, washed with methanol and
subjected to Soxhlet extraction for 24 h in acetone. The polymer P2
was redissolved in toluene and precipitated from methanol,
filtered, washed with methanol and dried. Mn=2.5.times.10.sup.4,
Mw=3.5.times.10.sup.4 g/mol, D=1.4. .sup.1H-NMR
(1,1,2,2-Tetrachloroethane-d.sub.2) (400 MHz) ppm 7.54-7.00 (m, 8H)
ppm 2.35 (t, 4H, J=7.5 Hz) ppm 1.36-1.21 (broad peak, 40H) ppm 0.89
(t, 6H, J=6.8 Hz). Elemental analysis (calcd): C, 73.21 (73.89); H,
7.60 (8.17).
EXAMPLE 1C
Preparation of poly
[(1,2-bis-(2'-thienyl)vinyl-5',5''-diyl)-alt-(5,5'-bis(3-tetradecylthioph-
en-2-yl)) (Polymer P3)
##STR00051##
Equimolar amounts of
bis(trimethylstannyl)trans-1,2-di(2-thienyl)ethylene (2) (0.50
mmol, 358 mg) and 5,5'-dibromo-4,4'-ditetradecyl[2,2']bithiophene
(7) (0.50 mmol, 259 mg) were dissolved in anhydrous chlorobenzene
(16.7 mL) followed by the addition of
tri(dibenzylideneacetone)dipalladium(0) (0.015 mmol, 14 mg) and
tri(o-tolyl)phosphine (0.03 mmol, 9 mg) under N.sub.2. The
resulting mixture was refluxed for 2 days under N2. Thereafter,
2-(trimethylstannyl)thiophene (0.2 mL) and 2-bromo-thiophene (0.2
mL) were added to endcap the polymer at the interval of 3 hours and
the reaction mixture was refluxed for an additional 6 hours. After
being cooled to room temperature, the reaction mixture was
precipitated into a mixture of methanol (300 mL) and hydrochloric
acid (10 mL, 2N) and stirred for 2 h at room temperature. The
polymer P3 was filtered, washed with methanol and subjected to
Soxhlet extraction for 24 h in acetone. The polymer P3 was
redissolved in toluene and precipitated from methanol, filtered,
washed with methanol and dried. Mn=1.7.times.10.sup.4 g/mol, D=1.8.
.sup.1H-NMR (1,1,2,2-Tetrachloroethane-d.sub.2) (400 MHz) ppm 7.04
(m, 8H) ppm 2.79 (m, 4H) ppm 1.70 (m, 4H) ppm 1.35 (broad peak,
44H) ppm 0.88 (t, 6H, J=6.6 Hz). Elemental analysis (calcd): C,
74.25 (73.94); H, 8.58 (8.90).
EXAMPLE 1D
Preparation of poly
[(1,2-bis-(2'-thienyl)vinyl-5',5''-diyl)-alt-(5,5'-bis(3-dodecylthiophen--
2-yl)] (Polymer P4)
##STR00052##
Equimolar amounts of
bis(trimethylstannyl)trans-1,2-di(2-thienyl)ethylene (2) (0.18
mmol, 120 mg) and 5,5'-dibromo-4,4'-didodecyl[2,2']bithiophene (8)
(0.18 mmol, 93 mg) were dissolved in anhydrous chlorobenzene (6 mL)
followed by the addition of tri(dibenzylideneacetone)dipalladium(0)
(0.005 mmol, 4 mg) and tri(o-tolyl)phosphine (0.01 mmol, 3 mg)
under N.sub.2. The resulting mixture was refluxed for 2 days under
N2. Thereafter, 2-(trimethylstannyl)thiophene (0.1 mL) and
2-bromo-thiophene (0.1 mL) were added to endcap the polymer at the
interval of 3 hours and the reaction mixture was refluxed for an
additional 6 hours. After being cooled to room temperature, the
reaction mixture was precipitated into a mixture of methanol (300
mL) and hydrochloric acid (10 mL, 2N) and stirred for 2 h at room
temperature. The polymer P4 was filtered, washed with methanol and
subjected to Soxhlet extraction for 24 h in acetone. The polymer P4
was redissolved in toluene and precipitated from methanol,
filtered, washed with methanol and dried. Mn=1.6.times.10.sup.4
g/mol, D=2.2. .sup.1H-NMR (1,1,2,2-Tetrachloroethane-d.sub.2) (400
MHz) ppm 7.03 (m, 8H) ppm 2.78 (m, 4H) ppm 1.70 (m, 4H) ppm 1.35
(broad peak, 36H) ppm 0.89 (t, 6H, J=6.6 Hz). Elemental analysis
(calcd): C, 73.30 (72.99); H, 8.35 (8.46).
EXAMPLE 1E
Preparation of poly
[(2,2'-bithiophene-2,5'-diyl)-alt-(3,3'-di-noctylsilylene-2,2'-bithiophen-
e-5,5'-diyl)] (Polymer P6)
##STR00053##
Equimolar amounts of 2,5'-bis(trimethylstannyl)-2,2'-bithiophene
monomer (9) (0.50 mmol, 0.246 g) and
5,5'-dibromo-3,3'-di-n-octylsilylene-2,2'-bithiophene (5) (0.50
mmol, 0.288 g) were dissolved in anhydrous toluene (10.0 mL)
followed by the addition of
tetrakis(triphenylphosphine)palladium(0) (0.025 mmol, 29 mg) under
N.sub.2. The resulting mixture was heated at 100.degree. C. for 2
days under N.sub.2. Thereafter, 2-(trimethylstannyl)thiophene (0.2
mL) and 2-bromo-thiophene (0.2 mL) were added to endcap the polymer
at the interval of 3 hours and the reaction mixture was heated at
100.degree. C. for an additional 6 hours. After being cooled to
room temperature, the reaction mixture was precipitated into a
mixture of methanol (300 mL) and stirred for 2 h at room
temperature. The polymer P6 was filtered, washed with methanol and
subjected to Soxhlet extraction for 24 h in acetone and dioxane
sequentially. The polymer P6 was redissolved in toluene and
precipitated from methanol, filtered, washed with methanol and
dried. Mn=1.05.times.10.sup.5 g/mol, D=4.05. .sup.1H-NMR
(Tetrachlorethane-d.sub.2) (400 MHz): ppm 7.17-7.00 (m, 6H) ppm
1.48-1.16 (m, 24H) ppm 0.94-0.83 (m, 10H). Elemental analysis
(calcd): C, 66.19 (66.15); H, 6.93 (6.94); S, 21.93 (22.07).
EXAMPLE 2
Device Fabrication
The semiconducting properties of polymers of the present teachings
were evaluated in two transistor architectures (bottom-gate top
contact FIG. 6a and top-gate bottom-contact FIGS. 6c and 7a). All
device fabrication processes, except metal evaporation and the film
drying steps, were performed under ambient conditions. Table 1
summarizes the structure, the material for the different
components, and the method of fabrication of the various devices
made.
TABLE-US-00001 TABLE 1 Device Con- Annealing Mobility S. No.
figuration Substrate Polymer Temperature Dielectric (cm.sup.2/Vs) 1
TGBC Glass P1 No annealing PMMA 0.8-2 .times. 10.sup.-2 2 TGBC
Glass P1 150.degree. C. PMMA 3-6 .times. 10.sup.-2 3 TGBC Glass P1
250.degree. C. PMMA 0.1-5 .times. 10.sup.-6 4 TGBC Glass P6
(comparative No annealing PMMA 1-4 .times. 10.sup.-4 example to P1)
5 TGBC Glass P6 (comparative 150.degree. C. PMMA 2-5 .times.
10.sup.-3 example to P1) 6 TGBC Glass P6 (comparative 250.degree.
C. PMMA 0.5-2 .times. 10.sup.-1 example to P1) 7 BGBC Silicon P2 No
annealing SiO.sub.2 3-6 .times. 10.sup.-2 8 BGBC Silicon P3 No
annealing SiO.sub.2 1-3 .times. 10.sup.-2 9 BGBC Silicon P4 No
annealing SiO.sub.2 0.8-1.1 .times. 10.sup.-1
EXAMPLE 2A
Fabrication of Top-gate Bottom-contact Transistors Based on
P(TS8TVT)
Top-gate bottom-contact (TGBC) TFTs were fabricated on glass (PGO
glass) and were used as received. Au source-drain contacts (30
nm-thick) were thermally-evaporated. These substrates were coated
with the semiconductor layer deposited by spin-coating
(concentration .about.5-10 mg/mL in CHCs mixture, 1500-2000 rpm,
film dried at 90.degree. C. for 30 seconds and were either used
as-is or annealed at 150.degree. C. or annealed at 250.degree. C.
for 1 hour as shown in Table 1, film thickness=10-30 nm). A 20-60
mg/ml solution of PMMA in a proprietary formulation was spincoated
(1500-2000 rpm) and the dielectric film was dried at 100.degree. C.
for 1 minute. The resulting dielectric thickness is 300-400 nm. The
device structure was completed by vapor deposition of patterned Au
gate contacts (-30 nm thick) through a shadow mask. Channel lengths
and widths are 25-75 .mu.m and 0.5-1.5 mm, respectively, to afford
W/L=20.
COMPARATIVE EXAMPLE 2B
Fabrication of Top-gate Bottom-contact Transistors Based on
P(TS8T2)
These devices were made analogous to the TGBC devices with
P(TS8TVT). Identical glass substrates with patterned S/D contacts
were prepared and the semi-conductor layer was deposited by spin
coating (conc. .about.5 mg/ml in 2-MeTHF, 1000-2000 rpm, film dried
at 90.degree. C. for 30 seconds and then either used as-is or
annealed at temperatures up to 250.degree. C. for 1 hour as shown
in Table 1, film thickness 10-30 nm). The same dielectric
formulation as above was used to give similar films of identical
thicknesses, and the devices were completed as above with
deposition of patterned Au gate contacts.
EXAMPLE 2C
Fabrication of Bottom-gate Top-Contact Transistors Based on
P(T2-12-TVT)
Bottom-gate top-contact (BGBC) thin film transistors (TFTs) were
fabricated on n.sup.++--Si substrates with a thermally grown
SiO.sub.2 (200 nm) layer, with photolithographically patterned Au
S/D electrodes of different channel dimensions ranging from W=350
.mu.m to 7 mm, and L=5 .mu.m to 100 .mu.m for a W/L of 70. These
substrates were treated with hexamethyldisilazane vapor overnight
before semiconductor deposition. All BGBC devices were completed
with P(T2-12-TVT) layer deposition by spin-coating (concentration
.about.5-10 mg/mL in DCB, 1000-2000 rpm, film dried in ambient at
.about.90.degree. C. for 30 seconds, film thickness=10-50 nm).
EXAMPLE 2D
Fabrication of Bottom-gate Top-contact Transistors Based on
P(T2-14-TVT)
These devices were fabricated in a process identical to Example 3C,
using P(T2-14-TVT) deposited under identical conditions as the
active layer to yield films of similar thicknesses.
EXAMPLE 2E
Fabrication of Bottom-gate Top-contact Transistors Based on
P(BDT12-TVT)
BGBC devices of P(BDT12-TVT) were fabricated analogous to Examples
3C and 3 D on identically prepared substrates After surface
treatment with HMDS, these BGBC devices were completed with
P(BDT12-TVT) layer deposition by spin-coating (concentration
.about.5-10 mg/mL in DCB, 2000-3000 rpm, film dried in ambient at
.about.90.degree. C. for 30 seconds, film thickness=10-50 nm).
EXAMPLE 3
Device Characterization
A dual-channel Keithley 2612 or a Keithley 4200 semiconductor
characterization system with 3 source measurement units (SMUs)
configured with preamplifiers was used to perform all electrical
characterizations of the fabricated transistors. The other major
component of the test system is a Signatone probe station. A
dark/metal box enclosure was used to avoid light exposure and to
reduce environmental noise.
Transistor carrier mobilities (.mu.) were calculated by standard
field effect transistor equations. In traditional
metal-insulator-semiconductor FETs (MISFETs), there is typically a
linear and saturated regime in the I.sub.DS vs V.sub.DS curves at
different V.sub.G (where I.sub.DS is the source-drain saturation
current, V.sub.DS is the potential between the source and drain,
and V.sub.G is the gate voltage).
At large V.sub.DS, the current saturates and is given by:
(I.sub.DS).sub.sat=(WC.sub.i/2L).mu.(V.sub.G-V.sub.t).sup.2 (1)
where L and W are the device channel length and width,
respectively, C.sub.i is the specific capacitance of the gate
insulator, and V.sub.t is the threshold voltage. Mobilities (.mu.)
were calculated in the saturation regime by rearranging equation
(1): .mu..sub.sat=(2I.sub.DSL)/[WC.sub.i(V.sub.G-V.sub.t).sup.2]
(2)
The threshold voltage (V.sub.t) can be estimated as the x intercept
of the linear section of the plot of V.sub.G versus
(I.sub.DS).sup.1/2.
Table 2 summarizes the hole mobilities of the P(TS8TVT) and as a
comparison the hole mobilities of P(TS8TVT) (devices from Examples
2A and 2B) measured (for different annealing temperatures for the
semiconductor) under ambient conditions.
TABLE-US-00002 TABLE 2 Annealing Temp Field Effect Mobility
(cm.sup.2/Vs) Polymer RT 150.degree. C. 250.degree. C. P(TS8TVT)
0.8-2 .times. 10.sup.-2 3-6 .times. 10.sup.-2 0.1-5 .times.
10.sup.-6 P(TS8T2) 1-4 .times. 10.sup.-4 2-5 .times. 10.sup.-3
0.5-2 .times. 10.sup.-1
The hole mobilities of the TGBC TFTs for the as-spun films of
P(TS8TVT) can vary between 0.8-2.times.10.sup.-2 cm.sup.2/Vs. These
data demonstrate P(TS8TVT) as a p-channel polymeric semiconductor
readily processable from conventional organic solvents. More
importantly, device performance was found negligibly improved by
the P(TS8TVT) semiconductor layer thermal annealing (T.sub.a). For
a film annealed at 150.degree. C. for example, the mobilities of
the resultant TFTs were between 3-6.times.10.sup.-2 cm.sup.2/Vs,
only a factor of 2-4 times better than the films without annealing.
Annealing at higher temperatures such as 250.degree. C. resulted in
degradation of FET performance with very little to no field effect
demonstrated. The yields of these devices with high T.sub.a were
poor, and mobilities recorded range from 0.1-5.times.10.sup.-6
cm.sup.2/Vs. FIG. 5 shows a typical transfer plot for a TGBC device
with P(TS8TVT), where the semiconductor was annealed at 150.degree.
C.
Devices of comparative example 2B (with the TS8T2 as the active
semi-conductor layer) showed poor hole mobilities
(1-4.times.10.sup.-4 cm.sup.2/Vs) for the as-is films, and a steady
improvement of orders of magnitude for the annealed films
(2-5.times.10.sup.-3 cm.sup.2/Vs for T.sub.a=150.degree. C., and
0.5-2.times.10.sup.-1 for T.sub.a=250.degree. C.).
BGBC devices with P(BDT12-TVT) (Example 2E) exhibited hole
mobilities of up to 0.06 cm.sup.2/Vs for the as-spun films, and
showed little improvement with different annealing treatments.
Devices that were annealed at 60.degree. C. for 30 minutes, showed
hole mobilities of up to 0.1 cm.sup.2/Vs, and further, devices that
were annealed at 100.degree. C. for 30 minutes showed hole
mobilities of up to 0.14 cm.sup.2/Vs, and even higher temperatures
(>160.degree. C.) resulted in a decrease in the observed
mobility.
As further example, BGBC devices with P(T2-14-TVT) (devices from
Example 2C) exhibited hole mobilities up to 0.03 cm.sup.2/Vs for
the as-spun films and showed no improvement with annealing to
temperatures up to 100.degree. C., beyond which the device
performance degraded, and this performance degradation correlates
with the endothermic transitions at 106.degree. C. observed on the
DSC traces for this polymer.
As further example, BGBC devices with P(T2-12-TVT) (devices from
Example 2D) exhibited hole mobilities up to 0.11 cm.sup.2/Vs for
the as-spun films. A typical transfer plot (p-type) is shown in
FIG. 7. It should be noted that those skilled in art would not have
expected high hole mobilities for the as-spun films, given that a
structurally similar polymer (PQT12) with a bithiophene instead of
the dithienylvinylene moiety has an order of magnitude lower
mobility for the as-spun films, and reached these high mobilities
only after the films are annealed at 120.degree. C.-140.degree. C.
for at least 30 minutes-1 hour. Ref. Ong, B. S. et at. J. Am. Chem.
Soc. 2004, 126, 3378-3379.
The present teachings encompass embodiments in other specific forms
without departing from the spirit or essential characteristics
thereof. The foregoing embodiments are therefore to be considered
in all respects illustrative rather than limiting on the present
teachings described herein. Scope of the present invention is thus
indicated by the appended claims rather than by the foregoing
description, and all changes that come within the meaning and range
of equivalency of the claims are intended to be embraced
therein.
EXAMPLE 4
Monomer Synthesis
All reagents were purchased from commercial sources and used
without further purification unless otherwise noted. Conventional
Schlenk techniques were used, and reactions were carried out under
N.sub.2 unless otherwise noted. NMR spectra were recorded on a
Varian 400MR spectrometer (.sup.1H, 400 MHz). Polymer molecular
weights were determined on Agilent 1200 series with refractive
index detector in THF at room temperature versus polystyrene
standards. The thermal characteristics of polymer were studied
using a differential scanning calorimeter (DSC) (Mettler Toledo,
DSC/823e/500/404) with a scanning rate of 10.degree. C./min.
Elemental analyses were performed at the National University of
Singapore. 5,5'-Dibromo-4,4'-bi(dodecyl)-2,2'-bithiophene;
5,5'-dibromo-4,4'-bi(octyl)-2,2'-bithiophene, (McCulloch, I.;
Heeney, M.; Genevicius, K.; MacDonald, I.; Shkunov, M.; Sparrowe,
D.; Tierney, S.; Wagner, R.; Zhang, W.; Chabinyc, M. L.; Kline, R.
J.; McGehee, M. D.; Toney, F. M. Nat. Mater. 2006, 5, 328),
benzo[1,2-b:4,5-b']dithiophene-4,8-dione (Beimling, P.;
Ko.beta.mehl, G. Chem. Ber. 1986, 119, 3198).
5,5'-bis(3-dodecyl-2-thienyl)-2,2'-dithiophene (Ong, B. S.; Wu, Y.;
Liu, P.; Gardner, S. J. Am. Chem. Soc. 2004, 126, 3378),
1,3-dibromo-5-(2-hexyldecyl)thieno[3,4-c]pyrrole-4,6-dione
(Nielsen, C. B.; BOrnholm, T. Org. Lett. 2004, 6, 3381),
2,7-dibromo-4,4-dihexadecylcyclopentadithiophene (Zhang, M.; Tsao,
H. K.; Pisula, W.; Yang, C. D.; Mishra, A. K.; Muellen, K. J. Am.
Chem. Soc. 2007, 129, 3472), 2,5-dibromo-3,4-didodecyl-thiophene
(Ashraf, R. S.; Klemm, E. J. Polym. Part A: Polym. Chem. 2005, 43,
6445), 4,8-didodecylbenzo-[1,2-b:4,5-b]-dithiophene (Pan, H.; Wu,
Y.; Li Y.; Liu, P.; Ong, B. S.; Zhu, S.; Xu, G. Adv. Funct. Mater.
2007, 17, 3574) and
2,5-bis(trimethylstannyl)-thieno[3,2-b]thiophene (Fuller, L. S.;
Iddon, B.; Smith, K. A. J. Chem. Soc. Perkin Trans. 1, 1997, 3465)
were prepared according to literature procedures.
EXAMPLE 4a
Preparation of 3-dodecyl-2-thiophenecarboxaldehyde (11)
##STR00054##
A solution of n-Butyllithium (1.6M in hexanes, 8 mL, 12.67 mmol)
was added dropwise at -78.degree. C. under N2 to a stirred solution
of 2-bromo-3-dodecylthiophene (10) (4 g, 12.07 mmol in 96 mL of
ether). During the whole addition, the reaction temperature was
kept at -78.degree. C. At this temperature, DMF (1.4 mL, 18.11
mmol) was slowly added and the mixture was allowed to warm to room
temperature. The mixture was poured into a 1 M aqueous solution of
NH.sub.4Cl and extracted with CH.sub.2Cl.sub.2. The organic layer
was washed with water, dried over Na.sub.2SO.sub.4, and evaporated
under reduced pressure. The residue was passed through a short
column (silica gel, hexane/ethylacetate, 9:1) to give a light
yellow liquid compound 11 in 87% yield. .sup.1H-NMR (DCM-d.sub.2,
400 MHz) ppm 0.88 (t, 3H, J=6.8 Hz) ppm 1.27 (m, 18H) ppm 1.67 (td,
2H, J=7.6 Hz, J=15.1 Hz) ppm 2.96 (t, 2H) ppm 7.04 (d, 1H, J=5.0
Hz) ppm 7.66 (d, 1H, J=5.0 Hz) ppm 10.04 (s, 1H).
EXAMPLE 4b
Preparation of (E)-1,2-bis(3-dodecylthienyl)ethylene (12)
##STR00055##
To a suspension of low-valent Ti prepared from TiCl.sub.4 (0.94 mL,
8.56 mmol) and Zn (1.12 g, 17.11 mmol) in 42 mL of dry THF under
N.sub.2 at 0.degree. C. was added a dry solution of 11 (2 g, 7.13
mmol) in 14 mL of dry THF. After 2 h of refluxing, the mixture was
cooled to room temperature, filtered to remove excess Zn,
evaporated, poured into water and extracted with CH.sub.2Cl.sub.2.
The organic phase was washed with water and dried over MgSO.sub.4.
After solvent removal, the crude solid was purified by column
chromatography (silica gel, hexane) to give a pale yellow solid
compound 12 in 75% yield. .sup.1H-NMR (CDCl.sub.3, 400 MHz) ppm
0.88 (t, 6H, J=6.8 Hz) ppm 1.31 (m, 36H) ppm 1.59 (td, 4H, J=7.4
Hz, J=14.7 Hz) ppm 2.65 (m, 4H) ppm 6.84 (d, 2H, J=5.2 Hz) ppm 6.99
(s, 2H) ppm 7.07 (d, 2H, J=5.2 Hz).
EXAMPLE 4c
Preparation of
(E)-1,2-bis[3-dodecyl-5-(trimethylstannyl)-2-thienyl]ethylene
(13)
##STR00056##
(E)-1,2-Bis(3-dodecylthienyl)ethylene (12) (10.4 mmol, 2.00 g) was
dissolved in anhydrous THF (43.2 mL) and cooled to -78.degree. C.
under nitrogen. n-Butyllithium (21.84 mmol, 13.7 mL) was then added
dropwise. The resulting solution was warmed to room temperature
over 30 min and stirred at that temperature for 3 h. The mixture
was then cooled to -78.degree. C. before trimethyltin chloride
(21.84 mmol, 4.35 g) in anhydrous THF (26 mL) was added dropwise.
After addition, the mixture was warmed to room temperature over 4 h
and stirred for additional 20 h at room temperature. The reaction
mixture was poured into saturated NH.sub.4Cl solution (100 mL) and
the aqueous layer was extracted with diethyl ether. The combined
organic layers were washed with water, dried over Na.sub.2SO.sub.4
and concentrated under reduced pressure. The crude solid was
recrystallized from ethanol to give desired product 13 in 73%
yield. .sup.1H-NMR (CDCl.sub.3, 400 MHz) ppm 0.36 (s, 18H) ppm 0.88
(t, 6H, J=6.9 Hz) ppm 1.30 (m, 36H) ppm 1.59 (td, 4H, J=7.3 Hz,
J=14.9 Hz) ppm 2.65 (m, 4H) ppm 6.94 (s, 2H) ppm 7.00 (s, 2H).
EXAMPLE 4d
Preparation of (E)-1,2-bis[3-dodecyl-5-bromo-2-thienyl]ethylene
(14)
##STR00057##
(E)-1,2-Bis(3-dodecylthienyl)ethylene (12) (1.34 g, 2.54 mmol) was
dissolved in 25/25 mL of anhydrous DMF/THF and cooled to 0.degree.
C. Then, NBS (0.99 g, 5.59 mmol) dissolved in 15 mL of anhydrous
DMF was added dropwise to the mixture and the reaction was
monitored by TLC. The reaction was quenched with water and
extracted with diethylether. After washing with water, the organic
phase was dried over Na.sub.2SO.sub.4 and concentrated.
Purification using column chromatography (silica gel, hexane) gave
bright yellow solid compound 14 in 78% yield. .sup.1H-NMR
(DCM-d.sub.2, 400 MHz) ppm 0.88 (t, 6H, J=6.8 Hz) ppm 1.28 (m, 40H)
ppm 2.58 (m, 4H) ppm 6.80 (s, 2H) ppm 6.83 (s, 2H).
EXAMPLE 4e
Preparation of (E)-1,2-bis(4-bromothienyl)ethylene (16)
##STR00058##
To a suspension of low-valent Ti prepared from TiCl.sub.4 (2.8 mL,
25.13 mmol) and Zn (3.29 g, 50.26 mmol) in 126 mL of dry THF under
N2 at 0.degree. C. was added a dry solution of 15 (4 g, 20.94 mmol)
in 42 mL of dry THF. After 2 h of refluxing, the mixture was cooled
to room temperature, filtered to remove excess Zn, evaporated,
poured into water and extracted with CH.sub.2Cl.sub.2. The organic
phase was washed with water and dried over MgSO.sub.4. After
solvent removal, the crude solid was washed with warm ethanol to
give a brown solid compound 16 in 80% yield. .sup.1H-NMR
(CDCl.sub.3, 400 MHz) ppm 6.94 (s, 2H) ppm 6.97 (d, 2H, J=1.4 Hz)
ppm 7.10 (d, 2H, J=1.1 Hz).
EXAMPLE 4f
Preparation of (E)-1,2-bis(4-dodecylthienyl)ethylene (17)
##STR00059##
A mixture of 16 (1.1 g, 3.14 mmol) and NiCl.sub.2(dppp) (0.17 g,
0.31 mmol) was degassed in a 2 necked RBF. Anhydrous THF (25 mL)
was then added to the mixture. C.sub.12H.sub.25MgBr (1M in THF, 8
mL, 8 mmol) was added dropwise to the reaction mixture and heated
at 60.degree. C. overnight. The reaction was quenched with 2N
aqueous HCl, extracted with CH.sub.2Cl.sub.2 and filtered through
celite. The residue was purified by column chromatography (silica
gel, hexane/CH.sub.2Cl.sub.2, 4:1) and recrystallized from hexane
to give a yellow solid compound 17 in 38% yield. .sup.1H-NMR
(DCM-d.sub.2, 400 MHz) ppm 0.88 (t, 6H, J=6.8 Hz) ppm 1.29 (m, 36H)
ppm 1.60 (td, 4H, J=7.2 Hz, J=14.6 Hz) ppm 2.55 (m, 4H) ppm 6.78
(s, 2H) ppm 6.88 (s, 2H) ppm 6.96 (s, 2H).
EXAMPLE 4g
Preparation of (E)-1,2-Bis[4-dodecyl-5-bromo-2-thienyl]ethylene
(18)
##STR00060##
(E)-1,2-bis(4-dodecylthienyl)ethylene (17) (0.62 g, 1.17 mmol) was
dissolved in 24/78 mL of anhydrous DMF/THF and cooled to 0.degree.
C. Then, NBS (0.46 g, 2.57 mmoL) dissolved in 15 mL of anhydrous
DMF was added drop wise to the mixture and the reaction was
monitored by TLC. The reaction was quenched with water and
extracted with diethylether. After washing with water, the organic
phase was dried over Na.sub.2SO.sub.4 and concentrated.
Purification using column chromatography (silica gel, hexane) gave
yellow solid compound 18 in 93% yield. .sup.1H-NMR (DCM-d.sub.2,
400 MHz) ppm 0.88 (t, 6H, J=6.8 Hz) ppm 1.29 (m, 36H) ppm 1.57 (dd,
4H, J=7.3 Hz, J=14.6 Hz) ppm 2.51 (m, 4H) ppm 6.75 (s, 2H) ppm 6.79
(s, 2H).
EXAMPLE 4h
Preparation of 2-(trimethylstannyl)-4-dodecyl-thiophene (20)
##STR00061##
To a stirred degassed homogeneous solution of 3-dodecyl thiophene
(19) (2 g, 7.92 mmol) in THF at -78.degree. C. was added LDA (4.75
ml, 9.51 mmol) drop wise. The mixture was stirred at -78.degree. C.
for 1 h, then trimethylstannylchloride dissolved in 9.5 ml of THF
was added, and the solution warmed to room temperature. Stirring
was continued for 2 h at room temperature. The mixture was washed
with saturated NaHCO.sub.3 and extracted with diethylether. The
organic layer was separated and dried over anhydrous sodium
sulphate and concentrated under reduced pressure to give desired
product 20 in 90% yield. .sup.1H-NMR (CD.sub.2Cl.sub.2, 400 MHz)
.delta. 7.19 (s, 1H), 7.02 (s, 1H), 2.63 (t, 2H), 1.62 (m. 2H),
1.2-1.4 (m, 18H), 0.88 (t, 3H), 0.34 (s, 9H).
EXAMPLE 4i
Preparation of 4, 4'''-didodecyl-2,2':5', 2'':5'',
2'''-quaterthiophene (21)
##STR00062##
5,5'-dibromo-2,2'-bithiophene and
4-dodecyl-3-(trimethylstannyl)thiophene (20) were degassed in a 100
ml 2-neck round bottom flask. 10 ml of anhydrous toluene was added
to the reaction mixture and refluxed at 100.degree. C. After
cooling, the reaction mixture was extracted using DCM, washed with
water, brine, dried over anhydrous sodium sulphate and concentrated
under reduced pressure. The crude mixture was purified using column
chromatography using hexane as eluant to give the desired product
21 as an orange solid. Yield: 44% (0.4852 g). .sup.1H-NMR
(CD.sub.2Cl.sub.2, 400 MHz) .delta. 7.06 (s, 2H), 6.86 (s, 2H),
7.08-7.11 (m, 4H), 2.60 (t, 4H), 1.65 (m, 4H), 1.2-1.4 (m, 36H),
0.89 (t, 6H).
EXAMPLE 4j
Preparation of: 5, 5'''-Dibromo-4, 4'''-Didodecyl-2,2':5', 2'':5'',
2'''-quaterthiophene (22)
##STR00063##
To a cooled solution of 21 in DMF/THF mixture at 0.degree. C. was
added NBS dissolved in 5 ml of DMF. The reaction mixture was
stirred overnight at room temperature. Then, the reaction mixture
was poured into water, extracted with DCM, washed with brine and
dried over anhydrous sodium sulphate to give desired product 22 in
87% yield. (0.524 g). .sup.1H-NMR (CD.sub.2Cl.sub.2, 400 MHz)
.delta. 7.09 (d, 2H), 7.03 (d, 2H), 6.92 (s, 2H), 2.55 (t, 4H),
1.55-1.65 (4H, m), 1.2-1.4 (m, 36H), 0.88 (t, 6H).
EXAMPLE 4k
Preparation of 5,
5'''-bis(trimethylstannyl)-3,3'''-didodecyl-2,2':5',2'':
5'',2'''-quaterthiophene (24)
##STR00064##
To a homogeneous degassed solution of quaterthiophene 23 (Ong, B.
S.; Wu, Y.; Liu, P.; Gardner, S. J. Am. Chem. Soc. 2004, 126, 3378)
in THF at -78.degree. C. was added LDA drop wise. The mixture was
stirred at -78.degree. C. for 1 h, then Me.sub.3SnCl dissolved in 2
ml of THF was added, and the solution was warmed to room
temperature. Stirring was continued for 2 h. The reaction mixture
was poured into saturated NH.sub.4Cl solution and then extracted
using DCM, washed with water, brine, dried over anhydrous sodium
sulphate and concentrated under reduced pressure to give desired
product 24 as a dark brown liquid. Yield: 93.8% (610 mg).
.sup.1H-NMR (CDCl.sub.3, 400 MHz) .delta. 7.13 (d, 2H), 7.03 (m,
4H), 2.80 (t, 4H), 1.66 (m, 4H), 1.2-1.4 (m, 36H), 0.87 (t, 6H),
0.38 (s, 18H).
EXAMPLE 4l
Preparation of
4,8-bis(2-ethylhexyl)-benzo[1,2-b:4,5-b']-dithiophene (26)
##STR00065##
To a suspension of benzo[1,2-b:4,5-b']dithiophene-4,8-dione (25)
(Beimling, P.; Ko.beta.mehl, G. Chem. Ber. 1986, 119, 3198) (4.9 g,
22.2 mmol) in 100 mL of THF was added 2-ethylhexyl magnesium
bromide (111 mL, 1M in diethyl ether). The mixture was then heated
at 60.degree. C. for 24 h., and cooled to r.t. following by adding
SnCl.sub.2 (13.47 g, 71.04 mmol) in 190 mL of 10% HCl. The mixture
was heated at 60.degree. C. for 24 h. THF was removed under reduced
pressure. The residure was dissolved in ether, washed with water,
sat. NaHCO.sub.3, brine and water. The organic layer was dried over
MgSO.sub.4 and then concentrated. Column chromatography with hexane
gave 1.2 g (13%) of desired product 26. .sup.1H-NMR (400 MHz,
CDCl.sub.3): ppm 7.46 (d, 2H, J=5.6 Hz), 7.42 (d, 2H, J=5.6 Hz),
3.18-3.06 (m, 4H), 1.97 (hep, 2H, J=6.4 Hz), 1.43-1.18 (m, 16H),
0.91-0.81 (m, 12H).
EXAMPLE 4m
Preparation of
2,6-(trimethylstannyl)-4,8-bis(2-ethylhexyl)benzo[1,2-b:4,5-b']-dithiophe-
ne (27)
##STR00066##
Benzodithiophene 26 (1.93 mmol, 0.8 g) was dissolved in anhydrous
THF (10 mL) and cooled to -78.degree. C. under nitrogen.
n-Butyllithium (4.05 mmol, 2.5 mL) was then added drop wise. The
resulting solution was continued stirring at -78.degree. C. for 3 h
and at r.t. for 1 h. The mixture was then cooled to -78.degree. C.
before trimethyltin chloride (4.05 mmol, 0.8 g) in anhydrous THF (5
mL) was added drop wise. After addition, the mixture was warmed
slowly to room temperature and stirred for additional 20 h at room
temperature. The reaction mixture was poured into saturated
NH.sub.4Cl solution (30 mL) and the aqueous layer was extracted
with diethyl ether. The combined organic layers were washed with
water, dried over Na.sub.2SO.sub.4 and concentrated under reduced
pressure to obtain cornpound 27 which become solid under long
vacuum drying in 94% yield. .sup.1H-NMR (400 MHz,
CD.sub.2Cl.sub.2): ppm 7.53 (s, 2H), 3.21-3.08 (m, 4H), 1.93 (hep,
2H, J=6.4 Hz), 1.44-1.2 (m, 16H), 0.93-0.82 (m, 12H), 0.44 (s,
18H). HPLC(CHCl.sub.3: MeOH 99:1): 98.6%.
EXAMPLE 4n
Preparation of
2,6-(trimethylstannyl)-4,8-didodecyl-benzo[1,2-b:4,5-b']-dithiophene
(20)
##STR00067##
Compound 28 (1.9 mmol, 1.0 g) was dissolved in anhydrous THF (20
mL) and cooled to -78.degree. C. under nitrogen. n-Butyllithium
(4.05 mmol, 2.5 mL) was then added drop wise. The resulting
solution was continued stirring at -78.degree. C. for 3 h and at
r.t. for 1 h. The mixture was then cooled to -78.degree. C. before
trimethyltin chloride (4.05 mmol, 0.8 g) in anhydrous THF (5 mL)
was added drop wise. After addition, the mixture was warmed slowly
to room temperature and stirred for additional 20 h at room
temperature. The reaction mixture was poured into saturated
NH.sub.4Cl solution (30 mL) and the aqueous layer was extracted
with diethyl ether. The combined organic layers were washed with
water, dried over Na.sub.2SO.sub.4 and concentrated under reduced
pressure to obtain compound 29 (1.44 g, 89% yield). .sup.1H-NMR
(400 MHz, CDCl.sub.3): ppm 7.49 (s, 2H), 3.20 (t, 4H, J=8 Hz), 1.81
(quin, 4H, J=8 Hz), 1.47 (quin, 4H, J=8 Hz), 1.37 (quin, 4H, J=8H),
1.26 (bs, 28H), 0.88 (t, 6H, J=8 Hz), 0.45 (s, 18H).
EXAMPLE 4o
Preparation of
(Z)-5,5'-bis(trimethylstannyl)-[1,2-bis(2'-thienyl)vinyl] (31)
##STR00068##
Cis-TVT 30 (0.52 mmol, 0.1 g) was dissolved in anhydrous THF (8.4
mL) and cooled to -78.degree. C. under nitrogen. n-Butyllithium
(1.09 mmol, 0.68 mL) was then added drop wise. The resulting
solution was warmed to room temperature over 30 min and stirred at
that temperature for 3 h. The mixture was then cooled to
-78.degree. C. before trimethyltin chloride (1.09 mmol, 0.22 g) in
anhydrous THF (5 mL) was added drop wise. After addition, the
mixture was warmed to room temperature over 4 h and stirred for
additional 20 h at room temperature. The reaction mixture was
poured into saturated NH.sub.4Cl solution (100 mL) and the aqueous
layer was extracted with diethyl ether. The combined organic layers
were washed with water, dried over Na.sub.2SO.sub.4 and
concentrated under reduced pressure. The crude solid was
recrystallized from ethanol to give desired compound 31 in 43%
yield. .sup.1H-NMR (CDCl.sub.3, 400 MHz) ppm 0.37 (s, 18H) ppm 7.09
(d, 4H, J=4.8 Hz) ppm 7.13 (d, 2H, J=3.4 Hz).
EXAMPLE 5
Polymer Synthesis
EXAMPLE 5A
Polymer P7
##STR00069##
Equimolar amounts of monomer 14 (0.23 mmol, 158 mg) and monomer 29
(0.23 mmol, 200 mg) were dissolved in anhydrous chlorobenzene (7.7
mL) followed by the addition of Pd.sub.2 dba.sub.3 (0.007 mmol, 6
mg) and tri(o-tolyl)phosphine (0.014 mmol, 4 mg) under N.sub.2. The
resulting mixture was refluxed for 2 days under N.sub.2.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated in methanol (300 mL) and
stirred for 2 h at room temperature. The polymer P7 was filtered,
washed with methanol and subjected to Soxhlet extraction for 24 h
in acetone. The polymer P7 was redissolved in toluene and
precipitated from methanol, filtered, washed with methanol and
dried. Mn=1.3.times.10.sup.4, Mw=8.6.times.10.sup.4, PDI=6.4.
.sup.1H-NMR (1,1,2,2-Tetrachloroethane-d.sub.2, 400 MHz) ppm 0.94
(m, 12H) ppm 1.33 (broad peak, 72H) ppm 1.78 (m, 4H) ppm 1.94 (m,
4H) ppm 2.78 (m, 4H) ppm 3.22 (m, 4H) ppm 7.11 (m, 2H) ppm 7.19 (m,
2H) ppm 7.54 (m, 2H). Anal. (calcd): C, 77.27 (77.65); H, 9.86
(10.16).
EXAMPLE 5B
Polymer P8
##STR00070##
Equimolar amounts of compound 14 (0.29 mmol, 200 mg) and
5,5'-distannyl [2,2]bithiophene (32) (0.29 mmol, 143 mg) were
dissolved in anhydrous chlorobenzene (20 mL) followed by the
addition of Pd.sub.2 dba.sub.3 (0.009 mmol, 8 mg) and
tri(o-tolyl)phosphine (0.02 mmol, 6 mg) under N.sub.2. The
resulting mixture was refluxed for 2 days under N.sub.2.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated in methanol (500 mL) and
stirred for 2 h at room temperature. The polymer P8 was filtered,
washed with methanol and subjected to Soxhlet extraction for 24 h
in acetone. The polymer P8 was redissolved in toluene and
precipitated from methanol, filtered, washed with methanol and
dried. Mn=9.7.times.10.sup.3, Mw=5.7.times.10.sup.4, PDI=5.9.
.sup.1H-NMR (1,1,2,2-Tetrachloroethaned.sub.2, 400 MHz) ppm 0.94
(m, 6H) ppm 1.34 (broad peak, 36H) ppm 1.73 (m, 4H) ppm 2.72 (m,
4H) ppm 7.01 (m, 4H) ppm 7.14 (m, 4H). Anal. (calcd): C, 72.43
(72.99); H, 8.25 (8.46).
EXAMPLE 5C
Polymer P9
##STR00071##
Equimolar amounts of
5,5'-Dibromo-4,4'-bi(tetradecyl)-2,2'-bithiophene (33) (0.17 mmol,
122 mg) and monomer 31 (0.17 mmol, 88 mg) were dissolved in
anhydrous chlorobenzene (6.5 mL) followed by the addition of
Pd.sub.2 dba.sub.3 (0.005 mmol, 4.7 mg) and tri(o-tolyl)phosphine
(0.01 mmol, 3.5 mg) under N.sub.2. The resulting mixture was
refluxed for 2 days under N.sub.2. 2-Bromothiophene and
2-tributylstannylthiophene were added as end cappers, with
2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated in methanol (300 mL) and
stirred for 2 h at room temperature. The polymer P9 was filtered,
washed with methanol and subjected to Soxhlet extraction for 24 h
in acetone. The polymer P9 was redissolved in THF and
reprecipitated from methanol, filtered, washed with methanol and
dried. Mn=1.6.times.10.sup.4, Mw=3.4.times.10.sup.4, PDI=2.1.
.sup.1H-NMR (1,1,2,2-Tetrachloroethane-d.sub.2, 400 MHz) ppm 0.93
(m, 6H) ppm 1.34 (broad peak, 44H) ppm 1.76 (m, 4H) ppm 2.84 (m,
4H) ppm 7.07 (m, 8H). Anal. (calcd): C, 74.67 (73.94); H, 8.44
(8.90).
EXAMPLE 5D
Polymer P10
##STR00072##
Equimolar amounts of monomer 14 (0.29 mmol, 200 mg) and monomer 34
(0.29 mmol, 150 mg) were dissolved in anhydrous chlorobenzene (20
mL) followed by the addition of Pd.sub.2 dba.sub.3 (0.009 mmol, 8
mg) and tri(o-tolyl)phosphine (0.02 mmol, 6 mg) under N.sub.2. The
resulting mixture was refluxed for 2 days under N.sub.2.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated in methanol (500 mL) and
stirred for 2 h at room ternperature. The polymer P10 was filtered,
washed with methanol, subjected to Soxhlet extraction for 24 h in
acetone and dried. Mn=1.1.times.10.sup.4, Mw=3.0.times.10.sup.4,
PDI=2.8. Anal. (calcd): C, 73.18 (73.94); H, 8.19 (8.90).
EXAMPLE 5E
Polymer P11
##STR00073##
Equimolar amounts of
2,5-bis(trimethylstannyl)-thieno[3,2-b]thiophene (35) (0.25 mmol,
116 mg) and monomer 14 (0.25 mmol, 170 mg) were dissolved in
anhydrous chlorobenzene (20 mL) followed by the addition of
Pd.sub.2 dba.sub.3 (0.008 mmol, 7.3 mg) and tri(otolyl)phosphine
(0.02 mmol, 6 mg) under N.sub.2. The resulting mixture was refluxed
for 2 days under N.sub.2. 2-Bromothiophene and
2-tributylstannylthiophene were added as end cappers, with
2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated in methanol (500 mL) and
stirred for 2 h at room temperature. The polymer P11 was filtered,
washed with methanol, subjected to Soxhlet extraction for 24 h in
acetone and dried. Mn=8.3.times.10.sup.3, Mw=4.3.times.10.sup.4,
PDI=5.2. Anal. (calcd): C, 72.12 (72.23); H, 7.79 (8.49).
EXAMPLE 5F
Polymer P12
##STR00074##
Equimolar amounts of monomer 18 (0.26 mmol, 180 mg) and
5,5'-distannyl-[2,2']bithiophene (32) (0.26 mmol, 128 mg) were
dissolved in anhydrous chlorobenzene (16 mL) followed by the
addition of Pd.sub.2 dba.sub.3 (0.008 mmol, 7.3 mg) and
tri(o-tolyl)phosphine (0.02 mmol, 6.1 mg) under N2. The resulting
mixture was refluxed for 2 days under N.sub.2. 2-Bromothiophene and
2-tributylstannylthiophene were added as end cappers, with
2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated in methanol (500 mL) and
stirred for 2 h at room temperature. The polymer P12 was filtered,
washed with methanol and subjected to Soxhlet extraction for 24 h
in acetone. The polymer P12 was redissolved in THF and precipitated
from methanol, filtered, washed with methanol and dried.
Mn=2.0.times.10.sup.4, Mw=4.2.times.10.sup.4, PDI=2.1. .sup.1H-NMR
(1,1,2,2-Tetrachloroethane-d.sub.2, 400 MHz) ppm 0.95 (t, 6H, J=6.8
Hz) ppm 1.35 (broad peak, 36H) ppm 1.75 (m, 4H) ppm 2.82 (m, 4H)
ppm 6.97 (d, 4H, J=6.9 Hz) ppm 7.12 (d, 2H, J=3.7 Hz) ppm 7.20 (d,
2H, J=3.6 Hz).
EXAMPLE 5G
Polymer P13
##STR00075##
Equimolar amounts of monomer 18 (0.26 mmol, 180 mg) and
2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (35) (0.26 mmol,
122 mg) were dissolved in anhydrous chlorobenzene (16 mL) followed
by the addition of Pd.sub.2 dba.sub.3 (0.008 mmol, 7.3 mg) and
tri(otolyl)phosphine (0.02 mmol, 6.1 mg) under N.sub.2. The
resulting mixture was refluxed for 2 days under N.sub.2.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated into a mixture of methanol
(500 mL) and stirred for 2 h at room temperature. The polymer P13
was filtered, washed with methanol and subjected to Soxhlet
extraction for 24 h in acetone. The polymer P13 was redissolved in
chlorobenzene and precipitated from methanol, filtered, washed with
methanol and dried. Mn=8.0.times.10.sup.3, Mw=1.3.times.10.sup.4,
PDI=1.6. .sup.1H-NMR (1,1,2,2-Tetrachloroethane-d.sub.2, 400 MHz)
ppm 0.95 (t, 611, J=6.8 Hz) ppm 1.35 (broad peak, 36H) ppm 1.76 (m,
4H) ppm 2.85 (m, 4H) ppm 6.99 (d, 4H, J=4.2 Hz) ppm 7.33 (s, 2H).
Anal. (calcd): C, 72.32 (72.23); H, 7.92 (8.49).
EXAMPLE 5H
Polymer P14
##STR00076##
Dibromothiopheneimide 36 (0.20 g, 0.37 mmol), monomer 34 (0.19 g,
0.37 mmol), Pd.sub.2 dba.sub.3 (0.010 g, 0.011 mmol), and
P(o-tolyl).sub.3 (0.007 g, 0.022 mmol) were added to the rbf and
degassed for 3 times. After that, chlorobenzene (12 mL) was added
and the mixture was stirred at 130.degree. C. for 2 days.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. The reaction solution was then added
dropwise to 400 mL methanol, filtered, and then subjected to
Soxhlet extraction with acetone. The polymer P14 recovered inside
the Soxhlet thimble was dissolved in toluene at 70.degree. C. and
precipitated once more in methanol. Mn=9.54.times.10.sup.3 g/mol,
D=1.9. Elemental analysis (calcd): C, 67.96 (67.92); H, 6.80
(6.95).
EXAMPLE 5I
Polymer P15
##STR00077##
Equimolar amounts of monomer 18 (0.22 mmol, 150 mg) and monomer 29
(0.22 mmol, 188 mg) were dissolved in anhydrous chlorobenzene (7.4
mL) followed by the addition of Pd.sub.2 dba.sub.3 (0.007 mmol, 6.4
mg) and tri(o-tolyl)phosphine (0.01 mmol, 3.1 mg) under N.sub.2.
The resulting mixture was refluxed for 2 days under N.sub.2.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated in methanol (300 mL) and
stirred for 2 h at room temperature. The polymer P15 was filtered,
washed with methanol and subjected to Soxhlet extraction for 24 h
in acetone. The polymer P15 was redissolved in THF and precipitated
from methanol, filtered, washed with methanol and dried.
Mn=2.4.times.10.sup.3, Mw=4.8.times.10.sup.3, PDI=2.0. .sup.1H-NMR
(1,1,2,2-tetrachloroethane-d.sub.2, 400 MHz) ppm 0.93 (m, 12H) ppm
1.41 (m, 72H) ppm 1.78 (m, 4H) ppm 1.95 (m, 4H) ppm 2.92 (m, 4H)
ppm 3.22 (m, 4H) ppm 7.02 (m, 4H) ppm 7.51 (m, 2H). Anal. (calcd):
C, 77.98 (77.65); H, 9.91 (10.16).
EXAMPLE 5J
Polymer P16
##STR00078##
Equimolar amounts of monomer 24 (0.15 g, 0.15 mmol) and monomer 18
(0.103 g, 0.15 mmol), together with Pd.sub.2 dba.sub.3 (0.004 g,
0.0045 mmol) and P-(o-tolyl).sub.3 (0.0027 g, 0.009 mmol) were
degassed in a 50 ml 2-neck round bottom flask. Anhydrous
chlorobenzene (5.6 ml) was then added to the mixture. The reaction
mixture was refluxed under nitrogen at 130.degree. C. for 48 h.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. The polymer P16 was precipitated in
methanol, filtered, subjected to Soxhlet extraction for 24 h in
acetone and then redissolved in chlorobenzene and reprecipitated
again in methanol. Mn: 1.5.times.10.sup.4, PDI: 1.83 Anal. (calcd):
C %:74.79 (74.56) H %:9.18 (9.30). 1H-NMR (C.sub.2H.sub.2Cl.sub.4,
400 MHz) 7.18 (br s, 2H), 7.09 (br s, 2H), 7.01 (br s, 2H), 6.93
(br s, 2H), 6.91 (br s, 2H), 2.79 (t, 8H), 1.2-1.5 (m, 80H) 0.88
(t, 1211).
EXAMPLE 5K
Polymer P17
##STR00079##
Monomer 37 (0.20 g, 0.32 mmol),
2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene 35 (0.15 g, 0.32
mmol), Pd.sub.2 dba.sub.3 (0.009 g, 0.010 mmol), and
P(o-tolyl).sub.3 (0.006 g, 0.019 mmol) were added to the two neck
rbf and degassed for 3 times. After chlorobenzene (16 mL) were
added, the mixture was stirred at 130.degree. C. for 36 h.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. The reaction mixture was cooled to room
temperature. The reaction solution was then added drop wise to 400
mL methanol, filtered, and then subjected to Soxhlet extraction
with acetone. The polymer P17 recovered inside the Soxhlet thimble
was redissolved in chlorobenzene at 70.degree. C. and
reprecipitated in methanol. Mn=1.03.times.10.sup.4 g/mol, D=1.7.
Elemental analysis (calcd): C, 70.86 (71.00); H, 7.46 (7.94).
EXAMPLE 5L
Polymer P18
##STR00080##
Equimolar amounts of monomer 22 (0.5 g, 0.606 mmol), monomer 13
(0.518 g, 0.606 mmol), Pd.sub.2 dba.sub.3 (0.0167 g, 0.018 mmol)
and P-(o-tolyl).sub.3 (0.011 g, 0.036 mmol) were degassed in a 50
ml schlenk tube. 6 ml of chlorobenzene was then added and the
mixture refluxed at 130.degree. C. for 2 days. 2-Bromothiophene and
2-tributylstannylthiophene were added as end cappers, with
2-bromothiophene added first followed by
2-tributylstannylthiophene. The crude polymer was precipitated in
methanol, filtered. After filtering, the polymer P18 was subjected
to Soxhlet extraction in acetone at 85.degree. C. The polymer P18
was then redissolved in chlorobenzene, reprecipitated in methanol
and dried. Mn: 2.7.times.10.sup.4, PDI: 4.4 Anal. (calcd): C
%:74.56 (74.56) H %:9.30 (9.17). 1H-NMR(C.sub.2H.sub.2C.sub.14, 400
MHz) 7.14 (br s, 4H), 7.08 (br s, 2H), 7.05 (br s, 2H), 6.98 (br s,
2H), 2.85, (t, 4H), 2.75 (t, 4H), 1.75 (m, 8H), 1.3-1.5 (m, 72H),
0.95 (m, 12H).
EXAMPLE 5M
Polymer P19
##STR00081##
Equimolar amounts of 5,5'-Dibromo-4,4'-bi(dodecyl)-2,2'-bithiophene
(38) (0.15 mmol, 100 mg) and monomer 13 (0.15 mmol, 128 mg) were
dissolved in anhydrous chlorobenzene (2 mL) followed by the
addition of Pd.sub.2 dba.sub.3 (0.005 mmol, 4.6 mg) and
tri(otolyl)phosphine (0.01 mmol, 3.1 mg) under N.sub.2. The
resulting mixture was refluxed for 2 days under N.sub.2.
2-Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated into a mixture of methanol
(300 mL) and stirred for 2 h at room temperature. The polymer P19
was filtered, washed with methanol and subjected to Soxhlet
extraction for 24 h in acetone. The polymer P19 was redissolved in
THF and precipitated from methanol, filtered, washed with methanol
and dried. Mn=1.3.times.10.sup.4, Mw=2.2.times.10.sup.4,
PDI=1.7.
.sup.1H-NMR (1,1,2,2-Tetrachloroethane-d.sub.2, 400 MHz) ppm 0.94
(m, 12H) ppm 1.34 (broad peak, 72H) ppm 1.75 (m, 8H) ppm 2.74 (m,
4H) ppm 2.84 (m, 4H) ppm 6.97 (s, 2H) ppm 7.05 (d, 4H, J=6.8 Hz).
Anal. (calcd): C, 76.67 (77.13); H, 9.72 (10.40).
EXAMPLE 5N
Polymer P20
##STR00082##
Equimolar amounts of 5,5'-dibromo-4,4'-di(octyl)-2,2'-bithiophene
(39) (0.28 mmol, 153.6 mg) and monomer 13 (0.28 mmol, 208.1 mg)
were dissolved in anhydrous chlorobenzene (5.2 mL) followed by the
addition of Pd.sub.2 dba.sub.3 (0.0084 mmol, 7.7 mg) and
tri(o-tolyl)phosphine (0.0168 mmol, 5.1 mg) under N2. The resulting
mixture was refluxed for 2 days under N.sub.2. 2-Bromothiophene and
2-tributylstannylthiophene were added as end cappers, with
2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated into a mixture of methanol
(300 mL) and stirred for 2 h at room temperature. The polymer P20
was filtered, washed with methanol and subjected to Soxhlet
extraction for 24 h in acetone. The polymer P20 was redissolved in
THF and precipitated from methanol, filtered, washed with methanol
and dried. Mn=6.4.times.10.sup.3, PDI=1.55. .sup.1H-NMR
(CDCl.sub.3, 400 MHz) ppm 0.89 (m, 12H) ppm 1.31 (m, 40H) ppm 1.67
(m, 8H) ppm 2.73 (m, 8H) ppm 6.92 (m, 6H). Anal. (calcd): C, 74.48
(74.75); H, 9.72 (9.28).
EXAMPLE 5O
Polymer P21
##STR00083##
Equimolar amounts of 40 (0.047 g, 0.135 mmol) and 27 (0.1 g, 0.135
mmol), together with Pd.sub.2 dba.sub.3 (0.00782 g, 0.0081 mmol)
and P(o-tolyl).sub.3 (0.00493 g, 0.0162 mmol) were degassed in a 50
ml schlenk tube. Anhydrous chlorobenzene (5 ml) was then added to
the mixture. The reaction mixture was refluxed under N.sub.2 at
130.degree. C. 2-Bromothiophene and 2-tributylstannylthiophene were
added as end cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. The reaction mixture was precipitated
in methanol and the crude polymer P21 was filtered and subjected to
Soxhlet extraction for 24 h in acetone and dried. Mn: 1640, PDI:
1.5. Anal. (calcd): C %:71.76 (71.71) H %:6.92 (7.02).
EXAMPLE 5P
Polymer P22
##STR00084##
Equimolar amounts of cyclopentadithiophene 41 (0.38 mmol, 300 mg)
and monomer 34 (0.38 mmol, 197 mg) were dissolved in anhydrous
chlorobenzene (12.7 mL) followed by the addition of Pd.sub.2
dba.sub.3 (0.011 mmol, 10.4 mg) and P(o-tolyl).sub.3 (0.02 mmol,
6.9 mg) under N.sub.2. The resulting mixture was refluxed for 2
days under N.sub.2. Bromothiophene and 2-tributylstannylthiophene
were added as end cappers, with 2-bromothiophene added first
followed by 2-tributylstannylthiophene. After being cooled to room
temperature, the reaction mixture was precipitated into a mixture
of methanol (500 mL) and stirred for 2 h at room temperature. The
polymer P22 was filtered, washed with methanol and subjected to
Soxhlet extraction for 24 h in acetone. The polymer P22 was
redissolved in chlorobenzene and reprecipitated from methanol,
filtered, washed with methanol and dried. Mn=3.6.times.10.sup.4,
PDI=2.5. .sup.1H-NMR (1,1,2,2-Tetrachloroethane-d.sub.2, 400 MHz)
ppm 0.95 (t, 6H, J=6.8 Hz) ppm 1.24 (broad peak, 56H) ppm 1.93 (m,
4H) ppm 7.01 (s, 2H) ppm 7.12 (broad peak, 6H). Anal. (calcd): C,
75.16 (75.12); H, 8.59 (9.15).
EXAMPLE 5Q
Polymer P23
##STR00085##
Equimolar amounts of monomer 42 (0.17 mmol, 100 mg) and monomer 13
(0.17 mmol, 145 mg) were dissolved in anhydrous chlorobenzene (1
mL) followed by the addition of Pd.sub.2 dba.sub.3 (0.005 mmol, 4.6
mg) and tri(o-tolyl)phosphine (0.01 mmol, 3.1 mg) under N.sub.2.
The resulting mixture was refluxed for 2 days under N2.
Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated into a mixture of methanol
(300 mL) and stirred for 2 h at room temperature. The polymer P23
was filtered, washed with methanol and subjected to Soxhlet
extraction for 24 h in acetone. The polymer P23 was redissolved in
THF and precipitated from methanol, filtered, washed with methanol
and dried. Mn=1.4.times.10.sup.4, PDI=2.0. .sup.1H-NMR
(1,1,2,2-tetrachloroethane-d.sub.2, 400 MHz) ppm 0.93 (m, 12H) ppm
1.34 (m, 72H) ppm 1.71 (m, 8H) ppm 2.71 (m, 4H) ppm 2.83 (m, 4H)
ppm 7.02 (m, 4H).
EXAMPLE 5R
Polymer P24
##STR00086##
Equimolar amounts of monomer 43 (0.24 mmol, 114 mg) and monomer 13
(0.24 mmol, 205 mg) were dissolved in anhydrous chlorobenzene (4.8
mL) followed by the addition of Pd.sub.2 dba.sub.3 (0.007 mmol, 6.6
mg) and tri(o-tolyl)phosphine (0.01 mmol, 4.4 mg) under N.sub.2.
The resulting mixture was refluxed for 2 days under N2.
Bromothiophene and 2-tributylstannylthiophene were added as end
cappers, with 2-bromothiophene added first followed by
2-tributylstannylthiophene. After being cooled to room temperature,
the reaction mixture was precipitated into a mixture of methanol
(300 mL) and stirred for 2 h at room temperature. The polymer P24
was filtered, washed with methanol and subjected to Soxhlet
extraction for 24 h in acetone. The polymer P24 was redissolved in
THF and precipitated from methanol, filtered, washed with methanol
and dried. Mn=3.5.times.10.sup.4, PDI=4.7. .sup.1H-NMR
(1,1,2,2-Tetrachloroethane-d.sub.2, 400 MHz) ppm 0.94 (m. 9H) ppm
1.35 (m, 54H) ppm 1.80 (m, 6H) ppm 2.83 (t, 4H, J=7.3 Hz) ppm 3.76
(m, 2H) ppm 7.20 (s, 2H) ppm 7.76 (s, 2H) ppm 7.85 (s, 2H).
Compound 43 as prepared according to Dierschke, F.; Jacob, J.;
Muellen, K. Synth. Met. 2006, 156, 433.
EXAMPLE 5S
Polymer P25
##STR00087##
Compound 43 (2.78 g. 5.87 mmol), 2-(tributylstannyl)thiophene (5.48
g, 14.69 mmol), Pd.sub.2(dba).sub.3 (0.32 g, 0.35 mmol) and
tri(o-tolyl)phosphine (0.21 g, 0.7 mmol) were added to the RBF and
degassed 3 times. The chlorobenzene (19.6 ml) was injected to the
RBF. The mixture was stirred at 130.degree. C. overnight. The
reaction mixture was quenched by H.sub.2O (50 mL) and extracted
with CHCl.sub.3 (50 mL.times.3). After washing with H.sub.2O, the
organic phase was dried over Na.sub.2SO.sub.4 and concentrated
under vacuum. Purification using column chromatography with 3 wt %
triethylamine in hexane as the eluent afforded 2.71 g (96%) of
product 44 (yellow solid). .sup.1H-NMR (CDCl.sub.3, 400 MHz):
7.78-7.77 (m, 4H), 7.48-7.47 (m, 2H), 7.19-7.16 (d, 2H), 3.68-3.64
(t, 2H), 1.67-1.62 (m, 2H), 1.30-1.24 (m, 18H), 0.89-0.85 (t,
3H).
##STR00088##
Compound 44 (2.61 g. 5.45 mmol), NBS (2.33 g, 13.07 mmol) were
dissolved in AcOH (54 ml) and CHCl.sub.3 (54 ml) and then stirred
at room temperature overnight. The reaction mixture was quenched by
H.sub.2O (50 ml) and extracted with CH.sub.2Cl.sub.2 (50
mL.times.3). After washing with H.sub.2O, the organic phase was
dried over Na.sub.2SO.sub.4 and concentrated under vacuum.
Purification using column chromatography with hexane as the eluent
afforded 3.12 g (90%) of product 45 (yellow solid). .sup.1H-NMR
(CDCl.sub.3, 400 MHz): 7.69 (s, 2H), 7.52-7.51 (d, 2H), 7.13-7.12
(d, 2H), 3.68-3.64 (t, 2H), 1.31-1.24 (m, 20H), 0.89-0.86 (t,
3H).
##STR00089##
Monomer 45 (200 mg, 0.31 mmol), monomer 13 (268 mg, 0.31 mmol),
Pd.sub.2 dba.sub.3 (8.6 mg, 0.009 mmol) and tri(o-tolyl)phosphine
(5.7 mg, 0.019 mmol) were added into 50 ml Schlenk tube and
degassed 3 times. Anhydrous chlorobenzene (6.3 ml) was then added
to the mixture. The reaction mixture was stirred at 100.degree. C.
overnight. The polymer P25 was precipitated in methanol, filtered
and subjected to the Soxhlet extraction in acetone at 85.degree. C.
The polymer P25 was then dissolved in chlorobenzene and
reprecipitated in methanol. .sup.1H-NMR (Tetrachloroethane-d2, 400
MHz): 7.86 (m, 4H), 7.29 (m, 2H), 7.12-7.03 (m, 4H), 3.75 (m, 2H),
2.74 (m, 4H), 1.75 (m, 6H), 1.49-1.35 (m, 54H), 0.95 (m, 9H). Mn:
8.2.times.10.sup.3, PDI: 1.48.
EXAMPLE 5T
Polymer P26
##STR00090##
Compound 46 (0.5 g. 0.76 mmol), 2-(tributylstannyl)thiophene (0.71
g, 1.89 mmol), Pd.sub.2(dba).sub.3 (41.7 mg, 0.046 mmol) and
tri(o-tolyl)phosphine (27.7 mg, 0.091 mmol) were added to the RBF
and degassed 3 times. The chlorobenzene (10 ml) was added to the
RBF. The mixture was stirred at 130.degree. C. overnight. The
reaction mixture was quenched by H.sub.2O (20 mL) and extracted
with CH.sub.2Cl.sub.2 (20 mL.times.3). After washing with H.sub.2O,
the organic phase was dried over Na.sub.2SO.sub.4 and concentrated
under vacuum. Purification using chromatography with hexane as the
eluent afforded 0.5 g (99%) yellow solid. .sup.1H-NMR (CDCl.sub.3,
400 MHz): 7.31-7.30 (d, 2H), 7.13-7.12 (d, 2H), 7.08-7.06 (t, 2H),
7.00 (s, 2H), 2.74-2.70 (t, 4H), 1.69-1.61 (m, 4H), 1.39-1.26 (m,
36H), 0.90-0.88 (t, 6H).
##STR00091##
Compound 47 (0.1 g. 0.15 mmol) was dissolved in DMF (0.5 ml) and
cooled to 0.degree. C. NBS (0.053 g, 0.30 mmol) dissolved in 0.5 ml
DMF was then added dropwise over 12 min to the mixture and the
reaction was monitored by TLC. The reaction mixture was
precipitated in methanol, filtered and dried to afford 0.1 g (81%)
of monomer 48 (yellow solid). .sup.1H-NMR (CDCl.sub.3, 400 MHz):
7.02-7.01 (d, 2H), 6.97 (s, 2H), 6.87-6.86 (d, 2H), 2.69-2.65 (t,
4H), 1.67-1.57 (m, 4H), 1.36-1.26 (m, 36H), 0.90-0.86 (t, 6H).
(M+):825.0. found: 825.1.
##STR00092##
Monomer 48 (200 mg, 0.24 mmol), monomer 13 (207 mg, 0.24 mmol),
Pd.sub.2 dba.sub.3 (7 mg, 0.007 mmol) and tri(o-tolyl)phosphine (4
mg, 0.014 mmol) were added into 50 ml Schlenk tube and degassed 3
times. Anhydrous chlorobenzene (8 ml) was then added to the
mixture. The reaction mixture was stirred at 130.degree. C. for 3
days. The polymer P26 was precipitated in methanol, filtered and
subjected to the Soxhlet extraction in acetone at 85.degree. C. The
polymer P26 was then dissolved in THF and reprecipitated in
methanol.
.sup.1H-NMR (Tetrachloroethane-d2, 400 MHz): 7.16-6.96 (m, 8H),
6.22 (s, 1H), 5.77 (s, 1H), 2.78-2.67 (m, 8H), 1.69-1.56 (m, 8H),
1.36-1.27 (m, 72H), 0.89-0.87 (m, 12H). Mn: 1.8.times.10.sup.4,
PDI: 2.20.
TABLE-US-00003 TABLE 3 Name Structure P7 ##STR00093## P8
##STR00094## P9 ##STR00095## P10 ##STR00096## P11 ##STR00097## P12
##STR00098## P13 ##STR00099## P14 ##STR00100## P15 ##STR00101## P16
##STR00102## P17 ##STR00103## P18 ##STR00104## P19 ##STR00105## P20
##STR00106## P21 ##STR00107## P22 ##STR00108## P23 ##STR00109## P24
##STR00110## P25 ##STR00111## P26 ##STR00112##
EXAMPLE 6
Device Fabrication
Devices were made in bottom gate bottom contact (BGBC) and top gate
bottom contact (TGBC) architectures by solution deposition. The
polymer solutions were prepared by solubilizing the polymers in
1,2-dichlorobenzene and heating them inside oven until they became
soluble (90-150.degree. C.). Solutions were then filtered using a
0.45 .mu.m filter. For partially soluble polymers dissolution was
supported by, sonication. All transistors were made and tested in
ambient environment.
EXAMPLE 6a
Fabrication of Bottom-gate Bottom-contact Transistors
(BGBC-TFT)
For preparing BGBC-TFT, heavily doped Si wafer was used as
substrate and gate electrode with 200 nm thermally grown SiO.sub.2
serving as gate dielectric. Source and drain electrode were made of
gold which were lithographically patterned. Before semi-conductor
deposition, the substrates were vapor treated with
hexamethyldisilazane (HMDS). Subsequently, semiconductor deposition
was done by spin coating or drop casting under the conditions
summarized in Table 4.
TABLE-US-00004 TABLE 4 Concentra- Sample tion Deposition Method
Deposition Condition P7 10 mg/ml Drop casting Drop on 50.degree. C.
hotplate P8 10 mg/ml Spin coating 2000 rpm, 1 minute P9 10 mg/ml
Spin coating 2000 rpm, 1 minute P10 5 mg/ml Spin coating 2000 rpm,
1 minute P11 5 mg/ml Spin coating 2000 rpm, 1 minute P12 10 mg/ml
Spin coating 2000 rpm, 1 minute P13 10 mg/ml Spin coating 2000 rpm,
1 minute P14 10 mg/ml Spin coating 2000 rpm, 1 minute P15 10 mg/ml
Spin coating 2000 rpm, 1 minute P16 10 mg/ml spin coating 2000 rpm,
1 minute P17 10 mg/ml spin coating 2000 rpm, 1 minute P18 30 mg/ml
spin coating 3500 rpm, 1 minute P19 20 mg/ml Spin coating 2000 rpm,
1 minute P20 20 mg/ml Spin coating 2000 rpm, 1 minute P21 5 mg/ml
Drop casting Drop on 90.degree. C. hotplate P22 10 mg/ml Spin
coating 1500 rpm, 1 minute P23 20 mg/ml Spin coating 2000 rpm. 1
minute P24 10 mg/ml Spin coating 2000 rpm, 1 minute P25 15 mg/ml
Spin coating 2000 rpm
EXAMPLE 6b
Fabrication of Top-gate Bottom-contact Transistors (TGBC-TFT)
For preparing TGBC-devices, two different types of substrates,
which were glass and PET (polyethylene terephthalate) substrates,
were used. For glass substrates, source/drain (S/D) gold pads were
deposited onto bare glass substrates by evaporation. Prior to
semiconductor deposition, the surface of the substrate was blown
dry to remove dust particles that might adhere to it. For
PET-substrates whose source-drain layouts were lithographically
patterned, substrate preparation started by rinsing them with
acetone to strip off the photo-resist layer as well as adhered
particles. Substrates were then heated using the hot plate
(90.degree. C. for 30 seconds) to further enhance the adhesion of
gold S/D lines.
Semiconductor deposition: Subsequently, semiconductor deposition
was done by spincoating based on the conditions summarized in Table
5. Annealing was done a glove box using a hot plate.
Dielectric deposition: Dielectrics solution was prepared by
dissolving 4 wt % polystyrene (PS) in isopropylacetate. It was then
deposited on top of semiconductor layer also by spincoating
applying the following conditions: 3600 rpm, 255 acc, 30 s;
90.degree. C., 30 s. After dielectric encapsulation, gold gate pads
were also deposited by evaporation. For glass substrates, prior to
IV measurement, S/D contact pads were exposed by dipping into
1,2-dichlorobenzene to dissolve the PS layer.
TABLE-US-00005 TABLE 5 Concentra- Dielectric Annealing Sample tion
Material temperature* Thickness Spin coat condition P9 10 mg/ml PS
RT [30]/[400] 1500 rpm; 120.degree. C. 10 s P12 10 mg/ml PS RT
[27]/[560] 2000 rpm; 100.degree. C. 30 s P12 10 mg/ml PS 80.degree.
C. 1 hour [27]/[560] 2000 rpm; 100.degree. C. 30 s P13 7 mg/ml PS
RT [26]/[560] 1000 rpm; 100.degree. C. 30 s P13 7 mg/ml PS
100.degree. C. 1 hour [26]/[560] 1000 rpm; 100.degree. C. 30 s P16
10 mg/ml PS RT [25]/[400] 1000 rpm; 100.degree. C. 30 s P17 10
mg/ml PS RT [40]/[400] 1000 rpm.; 100.degree. C. 30 s P24 5 mg/ml
PS RT [30]/[400] 1500 rpm; 130.degree. C. 30 s P19-PET 20 mg/ml PS
RT [60]/[400] 1000 rpm; 120.degree. C. 30 s P18-PET 15 mg/ml PS RT
[50]/[400] 1000 rpm; 130.degree. C. 30 s P24-PET 5 mg/ml PS RT
[30]/[400] 1500 rpm; 90.degree. C. 30 s P25-PET 15 mg/ml PS 2000
rpm P26-PET 15 mg/ml PS *room temperature
EXAMPLE 7
Device Characterization
Example 7a
BGBC-TFTs
The measurements were carried out on transistors with a channel
length of 5 .mu.m and channel width of 350 .mu.m. The results are
summarized in Table 6 below (Vd=drain voltage, Vg=gate
voltage).
I-V Measurement:
Measurement Condition for P7, P8, P9, P10, P11, P12:
Vd=-10V and -120V
Vg sweep from 20- to -90V
Measurement Condition for P14:
Vd=-10V and -60V
Vg sweep from 20 to -60V
Measurement Condition for Other Polymers:
Vd=-10V and -90V
Vg sweep from 20 to -90V
TABLE-US-00006 TABLE 6 Sample .mu. (cm.sup.2/Vs) V.sub.on (V)
On/Off P7-RT 1.05E-02 0 3.80E+03 P8-RT 1.14E-02 0 1.05E+05 P9-RT
1.23E-02 0 2.14E+04 P10-RT 2.41E-02 10 6.78E+05 P11-RT 3.47E-03 -25
2.31E+03 P12-RT 1.88E-02 0 2.49E+03 P13-RT 1.37E-01 10 1.11E+05
P14-RT 5.60E-06 -10 4.11E+02 P15-RT 1.20E-02 0 1.01E+05 P16-RT
2.85E-02 5 5.99E+04 P17-RT 2.92E-02 0 1.30E+04 P18-RT 1.62E-01 15
3.85E+04 P19-RT 2.80E-01 15 4.26E+04 P20-RT 1.62E-01 15 6.65E+03
P21-RT 2.67E-05 0 2.08E+02 P22-RT 7.76E-03 5 2.42E+04 P23-RT
6.03E-02 0 1.29E+03 P24-RT 1.12E-01 -15 1.41E+07 P25-RT 1.46E-03 5
6.23E+03
EXAMPLE 7b
TGBC-TFTs
I-V Measurement:
Measurement Condition for P18:
Vd=-80V and -1V
Vg sweep from 40 to -40V
Measurement Condition for P16:
Vd=-60V and -1V
Vg sweep from 60 to -60V
Measurement Condition for P24:
Vd=-60V and -1V
Vg sweep from 10 to -40V
Measurement Condition for P24-Pet:
Vd=-40V and -1V
Vg sweep from 10 to -40V
Measurement Condition for Other Polymers:
Vd=-60V and -1V
Vg sweep from 20 to -60V
The results are summarized in Table 7 below.
TABLE-US-00007 TABLE 7 Sample .mu. (cm.sup.2/Vs) V.sub.on (V)
On/Off P9-RT 1E-02 -8 2.79E+02 P12-RT 3.04E-02 -2 1.32E+02
P12-80.degree. C. 2.47E-02 -4 37 P13-RT 5.32E-02 -18 6
P13-100.degree. C. 7.85E-02 -6 33 P16-RT 2.42E-04 -5 7.55E01 P17-RT
3.10E-04 -10 14.6 P24-RT 2.14E-01 0 2.91E+03 P19-PET-RT 4.34E-02 --
1.37E+02 P18-PET-RT 0.309 20 2.08E+03 P24-PET-RT 0.138 2.5 5.03E+06
P25-PET-RT 1.09E-05 0 1.36E+02 P26-PET-RT 0.157 20 1.85E+04
EXAMPLE 7C
BGTC-TFT
TABLE-US-00008 TABLE 8 Sam- Dielectric Spin Coat .mu. ple Conc.
Material Condition (cm.sup.2/Vs) V.sub.on(V) On/Off P25 15 mg/ml
SiO.sub.2 2000 rpm 4.84E-04 0 2.04E03
* * * * *